EP4330201A1 - Method for manufacturing e-glass fibres from unprocessed mineral materials - Google Patents
Method for manufacturing e-glass fibres from unprocessed mineral materialsInfo
- Publication number
- EP4330201A1 EP4330201A1 EP22726489.2A EP22726489A EP4330201A1 EP 4330201 A1 EP4330201 A1 EP 4330201A1 EP 22726489 A EP22726489 A EP 22726489A EP 4330201 A1 EP4330201 A1 EP 4330201A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- calcium
- source
- glass
- cao
- boron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 40
- 239000011707 mineral Substances 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000003365 glass fiber Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 110
- 239000002994 raw material Substances 0.000 claims abstract description 70
- 239000011575 calcium Substances 0.000 claims abstract description 57
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 56
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000378 calcium silicate Substances 0.000 claims abstract description 37
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 37
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002844 melting Methods 0.000 claims abstract description 21
- 230000008018 melting Effects 0.000 claims abstract description 21
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 8
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000000155 melt Substances 0.000 claims abstract description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 65
- 239000011521 glass Substances 0.000 claims description 64
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 46
- 239000000292 calcium oxide Substances 0.000 claims description 42
- 235000012255 calcium oxide Nutrition 0.000 claims description 42
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 39
- 235000010755 mineral Nutrition 0.000 claims description 37
- 229910052796 boron Inorganic materials 0.000 claims description 28
- 229910052681 coesite Inorganic materials 0.000 claims description 25
- 229910052906 cristobalite Inorganic materials 0.000 claims description 25
- 229910052682 stishovite Inorganic materials 0.000 claims description 25
- 229910052905 tridymite Inorganic materials 0.000 claims description 25
- 229910021540 colemanite Inorganic materials 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 229910052810 boron oxide Inorganic materials 0.000 claims description 17
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 12
- 229910021538 borax Inorganic materials 0.000 claims description 12
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 12
- 239000004328 sodium tetraborate Substances 0.000 claims description 12
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 12
- 235000019738 Limestone Nutrition 0.000 claims description 10
- 239000006028 limestone Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 9
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 8
- 239000006063 cullet Substances 0.000 claims description 8
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002557 mineral fiber Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910052903 pyrophyllite Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000012681 fiber drawing Methods 0.000 claims description 3
- -1 kaolin Chemical compound 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910021539 ulexite Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000011491 glass wool Substances 0.000 claims description 2
- 239000011490 mineral wool Substances 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 51
- 229910002092 carbon dioxide Inorganic materials 0.000 description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000000156 glass melt Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- IQDXNHZDRQHKEF-UHFFFAOYSA-N dialuminum;dicalcium;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IQDXNHZDRQHKEF-UHFFFAOYSA-N 0.000 description 6
- 230000004927 fusion Effects 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005816 glass manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000006060 molten glass Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000007670 refining 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
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 102000011045 Chloride Channels Human genes 0.000 description 1
- 108010062745 Chloride Channels Proteins 0.000 description 1
- 229910017356 Fe2C Inorganic materials 0.000 description 1
- 229910021537 Kernite Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 201000010001 Silicosis Diseases 0.000 description 1
- 241001111950 Sonora Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000010292 electrical insulation Methods 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
- 238000000605 extraction Methods 0.000 description 1
- 230000010006 flight Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000005070 ripening Effects 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
-
- 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
- C03C13/00—Fibre or filament compositions
- C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
-
- 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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
Definitions
- the invention relates to the field of melting a mixture of raw materials, in particular for the manufacture of glass fibers, in particular glass fibers E-glass.
- E-glass yarn is not only used in the textile industry but also for the reinforcement of composite elements.
- E-glass fiber thus has a low thermal conductivity.
- the fiber can withstand temperatures of over 600°C and is non-combustible. In addition, it has excellent chemical resistance.
- E-glass fibrous products are resistant to oils, solvents, and most chemical agents. In addition, they are rot-proof.
- the E-glass yarn is also insensitive to variations in temperature and humidity and its coefficient of expansion is low.
- E-glass fiber products are also particularly resistant to abrasion and vibrations, and have excellent flexibility.
- Glass yarn has a higher specific strength (tensile strength/density) than steel. This characteristic makes it possible today to develop glass yarns that will reinforce high-performance composites.
- E-glass is obtained by melting a bath of raw material comprising silica, lime, kaolin, a source of boron such as borax or boric acid and possibly dolomite, the basic components being judiciously chosen to provide a glass composition producing fibers which combine flexibility and strength under mechanical traction as to heat, to chemical agents as to electric potential.
- the choice of the raw materials mentioned above is necessary to obtain a good quality of glass, in particular after its fiber drawing.
- the properties judged to be essential mention may be made in particular of the yield of the melting (ratio between the quantity of glass produced and the quantity of raw materials charged), the quality of the refining which results in a minimal number of residual bubbles in the glass, the homogeneity of the glass (in particular the homogeneity in S1O2), as well as the number of unmelted particles.
- the energy consumption energy required to melt the mixture of raw materials can also be an element to be taken into account.
- glass is usually prepared by melting in a furnace raw materials comprising silica and at least one alkaline earth (to give the glass resistance to hydrolysis) in the form of limestone ( calcium carbonate).
- An alumina carrier such as kaolin
- a boron carrier for example borax or boric acid
- boric acid or borax As described in application EP1886978A1.
- the carbonate(s) give off carbon dioxide, the bubbles of which contribute to the mixing of the mass being melted.
- the elimination of bubbles in the glass may also require the addition of a refining agent such as sodium or calcium sulphate, the release of sulfur oxide from which brings the residual bubbles of carbon dioxide and carbon dioxide to the surface of the glass. water.
- a refining agent such as sodium or calcium sulphate
- the CO2 emission due only to the raw materials is generally l 15 to 20% of the total mass of raw materials used.
- Carbon dioxide is a greenhouse gas and it is desirable to develop glass manufacturing processes that generate as little CO2 as possible for environmental reasons, while leading to good quality glass at an acceptable cost.
- the object of the present invention is to contribute to solving such a technical problem by proposing a process for the manufacture of E-glass for which the CO2 emissions are effectively reduced, based on all the steps leading to the formation of the glass fiber and for which the material transformation steps before the melting of the bath have been optimized.
- the present invention relates to a process for manufacturing E-glass fiber having a target composition, comprising the fusion of a mixture of raw materials constituting a fusion bath, said target composition meeting the following criteria, in weight percentages:
- - CaO between 20 and 35%, preferably between 20 and 30% - Al2O3: between 10 and 20%, preferably between 12 and 18%
- - MgO less than 2%, preferably between 0 and 1%
- the process being characterized in that it comprises the following steps: a) the raw materials of said fusion bath are selected, including at least: - a source of silicon chosen in particular from silica, E-glass cullet or recycled mineral fibers or their mixture, preferably silica, a source boron preferably chosen from borax or a boron and calcium oxide, in particular colemanite, or a boron, sodium and calcium oxide, in particular ulexite and/or a boron and sodium oxide such as tincalconite and/or kernite, or mixtures thereof, in particular colemanite represents at least 70% by weight, preferably at least 80% by weight of all the sources of boron, more preferably a mixture of borax and colemanite.
- a source of silicon chosen in particular from silica, E-glass cullet or recycled mineral fibers or their mixture, preferably silica, a source boron preferably chosen from borax or a boron and calcium oxide, in particular
- At least one source of calcium selected from a mixed oxide of calcium with at least one element selected from the group consisting by Si, Al, in particular a calcium silicate and/or a calcium aluminum silicate, optionally an additional source of aluminum such as kaolin, optionally hydrated alumina or pyrophyllite, optionally limestone CaCC> 3 or calcium hydroxide Ca(OH)2 or quicklime CaO, said calcium source(s) being natural mineral matter, that is to say coming from a natural geological environment and unprocessed, b) the composition of said natural calcium source(s) is determined, c) on the basis of said composition(s) determined according to point b), the quantities of said raw materials necessary to obtain a glass of said target composition are determined, d) the said materials are mixed according to the said quantities, e) the melting, the fiber drawing of the said mixture and its cooling are carried out under the conditions allowing the production of the said glass fibres.
- a source of calcium selected from a mixed oxide of calcium with at least one element selected from the group consist
- Said source of calcium is a natural mineral calcium silicate comprising, by weight percentage, at least 30% by weight of S1O2 and at least 30% by weight of CaO, S1O2 and CaO together representing more than 70% and preferably more than 75% or even more than 80% of said calcium silicate.
- - Said source of calcium is a natural mineral material having the following composition, in percentages by weight:
- - CO2 between 0 and 20%, for example between 0 and 15% - less than 5% of other oxides, preferably less than 3% of other oxides.
- Said source of calcium is a natural mineral calcium aluminum silicate comprising, in weight percentage, more than 30% by weight of S1O2, more than 15% by weight of CaO and more than 20% of ALCb, S1O2, CaO and
- - Said source of calcium is a natural mineral material having the following composition, in weight percentages: - S1O2: between 40 and 60%, preferably between 45 and 55%,
- - CaO between 10 and 30%, preferably between 12 and 20%
- Said source of boron comprises and preferably consists essentially, or even consists of a boron and calcium oxide comprising, in percentage by weight, more than 30% of B2O3 and more than 20% by weight of CaO.
- the source of boron consists mainly of an oxide of boron and calcium and in particular colemanite.
- said boron and calcium oxide, in particular colemanite represents more than 80%, preferably more than 85% or even more than 90% of the total weight of the boron source.
- only said one oxide of boron and calcium is used as source of boron.
- a mixture of an oxide of boron and calcium such as colemanite can be used.
- borax in which said boron and calcium oxide predominates, in particular the borax/boron and calcium oxide mass ratio of which is less than 0.2, or even less than 0.1.
- a source of calcium is calcium aluminum silicate.
- a source of calcium is constituted by a silicate of aluminum and calcium.
- the calcium source comprises a mixture of a calcium aluminum silicate and a calcium silicate.
- the source of calcium is a mixture of aluminum and calcium silicate and a calcium silicate.
- - Boron source includes colemanite and calcium source includes calcium aluminum silicate.
- a source of boron is an oxide of boron and calcium, in particular colemanite, and the source of calcium comprises and preferably consists of an aluminum and calcium silicate and a calcium silicate.
- the source of boron consists mainly of or consists of colemanite and the source of calcium consists of a mixture of aluminum and calcium silicate and a calcium silicate as previously described.
- - Said bath comprises a calcium silicate, an aluminum and calcium silicate and a source of boron consisting of a boron and calcium oxide, in particular colemanite.
- All the silicates present in the bath represent more than 30% of the total weight of said bath, preferably more than 35%, or even more than 40% or even more than 45% of the total weight of said bath, or even more than 50% of the total weight of said bath.
- the mixture of raw materials contains less than 12% by weight of CO2, preferably less than 10% of CO2, even more preferably less than 5% of CO2.
- recycled E-glass cullet or mineral fibers in particular recycled glass wool or recycled rock wool, are introduced into the molten pool, the recycled E-glass cullet or recycled mineral fibers representing preferably between 10 and 50% of the total weight of the melt.
- the recycled mineral fibers have the following composition: S1O2: between 30 and 50%, preferably between 35 and 45%,
- Na20 between 0 and 10%, preferably between 0.4 and 7%
- CaO between 10 and 35%, preferably between 12 and 25%,
- MgO between 1 and 15%, preferably between 5 and 13%
- AI2O3 between 10 and 27%
- K2O between 0 and 2%, preferably between 0 and 1%
- Iron oxide between 0.1 and 3%
- other oxide(s) between 0 and 5% cumulatively, preferably less than 3%, the remainder being made up of unavoidable impurities.
- the invention also relates to the mixture of raw materials described above.
- the raw materials are selected in such a way that in the final composition of the E-glass according to the invention:
- the B203/(Na20+K20) mass ratio is between 5 and 15, more preferably is between 6 and 10.
- the B203/(Na20+K20+Mg0) mass ratio is between 4.0 and 8.0.
- a low alkali content makes it possible not to degrade the dielectric performance of the glass with a constant boron content and a low magnesium content makes it possible not to raise the temperature of the liquidus of the glass.
- the mixture of raw materials according to the invention is intended to be heated to a temperature and under conditions allowing its melting in order to obtain a glass corresponding to said target composition.
- the originality of the present invention lies in the choice of raw materials. Indeed, it was discovered that it was possible to use natural mineral oxides, that is to say under their initial geological composition after their extraction from their deposit, including their possible impurities, in particular without chemical alteration aimed at modifying the initial composition, that is to say mineral materials not chemically transformed, as a source of calcium and possibly of aluminium, this choice advantageously leading to a reduction in the release of CO2 during the fusion reaction.
- the basis is initially based on the exact composition of these untransformed geological mineral materials, as determined precisely by any suitable technique (for example chemical analysis, X-ray diffraction, etc.) for determine the composition of the initial bath.
- the necessary proportions of the other components of said bath are calculated to arrive at a target composition of the final glass, so as to minimize the quantity of CO2 released, such as than measured on all the steps leading to the formation of the glass, and not only on the basis of the final melting step.
- said mineral oxides can of course undergo steps prior to their use as raw material for fusion, but without chemical transformation, such as crushing, screening, magnetic separation, washing or even flotation or any other physical separation, provided that it does not or substantially change the chemical composition of the initial mineral compound.
- the mixture of raw materials is introduced into the mixture of raw materials.
- the sum of the weight of carbonate(s) is less than 20%, and preferably less than 10%, and preferably less than 5%, and preferably less than 1% by weight, or even zero in the mixture of raw materials.
- the mixture of raw materials is free of any carbonate. It is advantageously capable of giving off substantially no carbon monoxide during its heating and its melting into glass, for example less than 2% or less than 1%.
- the Si carrier is very preferably introduced into the mixture of raw materials in the form of sand.
- the calcium carrier is provided in the form of a calcium silicate and/or a calcium aluminum silicate.
- the Al carrier can advantageously be introduced into the mixture of raw materials in the form of a calcium and aluminum silicate, identical to or different from the previous one.
- Each feedstock is introduced into the feedstock mixture in an amount such that the mole percentage of its cation (such as Si, Ca, Al, B, etc.) relative to the sum of moles of all cations is the same as in the final drink.
- the raw materials of the mixture are chosen to lead to a glass whose target composition falls within the scope (the percentage ranges of the different oxides) described above.
- the mixture of raw materials is heated until a molten glass is obtained, usually in a furnace.
- the temperature is heated more or less high and for more or less time depending on the quality of the glass you are looking for, in particular according to the degree of tolerance of unmelted particles (called "unmelted") and bubbles.
- the maximum heating temperature of molten glass is between 1400 and 1700°C.
- glass melting techniques well known to those skilled in the art. This transformation can be carried out in any type of oven such as an electric oven with electrodes, a furnace with overhead burners such as a furnace with transverse burners or a loop furnace, a furnace with submerged burners.
- the mixture of raw materials in particular pulverulent, can possibly be humidified before introduction into a furnace in order to reduce the flights of raw materials in the furnace due to the currents of combustion gases.
- the mixture of raw materials if necessary humidified, can be introduced into a furnace in a powder state, which implies that each raw material it contains is in a powder state.
- the mixture of raw materials moistened if necessary, can be introduced into a furnace in the state of composition comprising cullet and the mixture of raw materials, the latter being powdery if necessary.
- the mixture of raw materials may not be shaped by mechanical pressure. It is also not necessary to use a technique for granulating the raw material according to which the material is put into rotation (in particular in a tank of the rotating drum type) generally in the presence of a binder so as to lead to pellets.
- the mixture of raw materials is brought under air in a platinum crucible in 1 hour up to 1400°C then until the glass melts at 1500°C with a one-hour plateau at the maximum temperature.
- the amount of CO2 released is 155 grams.
- Example 2 In this example the mixture of raw materials is this time as described in Table 3 below.
- Example 1 the mixture of raw materials is brought under air in a platinum crucible in 1 hour up to 1400° C. then until the glass melts at 1500° C. with a one-hour plateau at the temperature maximum.
- the amount of CO2 released this time is 94 grams, a decrease of 40% compared to the reference example.
- the mixture of raw materials is this time as described in Table 4 below.
- this initial mixture we introduced as a reagent, to replace the limestone, a natural mineral matter of a calcium silicate directly from a quarry located in Sonora.
- This material is introduced directly, without any chemical transformation and after simple grinding aimed at adapting the particle size, mixed with the other constituents in proportions adjusted accordingly to obtain a glass with a composition very close to that of glass.
- reference example 1 This material is introduced directly, without any chemical transformation and after simple grinding aimed at adapting the particle size, mixed with the other constituents in proportions adjusted accordingly to obtain a glass with a composition very close to that of glass.
- Example 1 the mixture of raw materials is brought under air in a platinum crucible in 1 hour up to 1400° C. then until the glass melts at 1500° C. with a one-hour plateau at the temperature maximum. No CO2 release is observed for this example.
- the mixture of raw materials is this time as described in Table 5 below.
- this initial mixture was introduced as reagent, to replace all the limestone, mineral matter comprising a mixture of calcium silicate according to Example 3 and calcium silicate and natural aluminum of Example 2.
- composition in oxides of this mineral matter is given below.
- Example 5 As for Example 1, the mixture of raw materials is brought under air in a platinum crucible in 1 hour up to 1400° C. then until the glass melts at 1500° C. with a one-hour plateau at the temperature maximum. No release of CO2 is observed for this example.
- Example 5 As for Example 1, the mixture of raw materials is brought under air in a platinum crucible in 1 hour up to 1400° C. then until the glass melts at 1500° C. with a one-hour plateau at the temperature maximum. No release of CO2 is observed for this example.
- Example 5 Example 5:
- the mixture of raw materials is this time as described in Table 6 below.
- Example 1 the mixture of raw materials is brought under air in a platinum crucible in 1 hour up to 1400° C. then until the glass melts at 1500° C. with a one-hour plateau at the temperature maximum. No CO2 release is observed for this example.
- the mixture of raw materials is this time as described in Table 7 below.
- Example 1 the mixture of raw materials is brought under air in a platinum crucible in 1 hour up to 1400° C. then until the glass melts at 1500° C. with a one-hour plateau at the temperature maximum.
- the amount of CO2 released this time is 30 grams, a decrease of 81% compared to the reference example.
- the mixture of raw materials is this time as described in Table 8 below.
- Example 8 As for Example 1, the mixture of raw materials is brought under air in a platinum crucible in 1 hour up to 1400° C. then until the glass melts at 1500° C. with a one-hour plateau at the temperature maximum. The amount of CO2 released this time is 44 grams, a decrease of 72% compared to the reference example.
- Quantity of sand this is the quantity of sand used compared to reference example 1 (in percentage weight saved).
- reducing the quantity of sand used in favor of other mineral materials such as natural silicates makes it possible to reduce the energy to melt the glass, the most refractory raw material in the bath generally being silica.
- the number of bubbles per kilogram of molten glass is measured at 1410° C. for 240 minutes. The higher this index, the better the quality of ripening.
- the quality index is proportional to the S1O2 homogeneity (as measured by microprobe/EDS) of the molten glass at 1410°C for 240min.
- Homogeneity is measured by a series of measurements of the amount of S1O2 at different points in the glass and a standard deviation is then determined.
- This measurement corresponds to the energy required to melt the mixture of raw materials, as measured by DSC (as a percentage saved compared to the reference example 1)
- Example 2 according to the invention shows that the use of a natural calcium and aluminum silicate in combination with colemanite makes it possible to obtain a glass quality and especially with a low degree of unmelted, and even lower than the reference, which is essential for its use. Such a result appears surprising, if we look at the melting point of colemanite (around 1100°C) used in combination with a calcium and aluminum silicate in the melt.
- Example 3 the use of a natural calcium silicate in combination with colemanite has particular advantages and in particular a very strong reduction in the quantity of sand required, improved homogeneity and a certain energy gain but in return the presence of a greater quantity of unmelted particles than the reference.
- MgO, Na20, Fe203 and K2O remain extremely low, despite the use of unprocessed mineral materials in the melt. It is observed in particular that the MgO levels and the Na20 + K2O sum are between 0 and 1% and an Fe203 level of less than 0.5% in the composition of the final glass, which also makes it possible to guarantee low resistivity. electric glass.
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Abstract
The invention relates to a method for manufacturing E-glass fibres having a target composition, comprising melting a mixture of raw materials constituting a melt, including at least one calcium source selected from a mixed oxide of calcium with at least one element selected from the group consisting of Si and Al, in particular a calcium silicate and/or an aluminium and calcium silicate, said calcium source or sources being natural mineral materials, i.e. unprocessed mineral materials originating from a natural geological environment.
Description
DESCRIPTION DESCRIPTION
Titre : PROCEDE DE FABRICATION DE FIBRES DE VERRE-E A PARTIR DE MATIERES MINERALES NON TRANSFORMEES L’invention concerne le domaine de la fusion d’un mélange de matières premières, en particulier pour la fabrication de fibres de verre, en particulier de fibres de verre E. Le fil de verre E est non seulement utilisé dans l’industrie textile mais aussi pour les renforts des éléments composites. Title: METHOD FOR MANUFACTURING E-GLASS FIBERS FROM UNPROCESSED MINERAL MATERIALS The invention relates to the field of melting a mixture of raw materials, in particular for the manufacture of glass fibers, in particular glass fibers E-glass. E-glass yarn is not only used in the textile industry but also for the reinforcement of composite elements.
Ses excellentes propriétés d’isolation électrique, même à faible épaisseur, combinées à sa résistance mécanique et son comportement à différentes températures, ont été à la base des premières applications du fil de verre E. Its excellent electrical insulation properties, even at low thickness, combined with its mechanical resistance and its behavior at different temperatures, were the basis of the first applications of E-glass yarn.
La fibre de verre E possède ainsi une faible conductivité thermique. La fibre peut résister à des températures de plus de 600 °C et est incombustible. En outre elle présente une excellente résistance chimique. Les produits fibreux en verre E résistent aux huiles, aux solvants, et la majorité des agents chimiques. De plus, ils sont imputrescibles. Le fil de verre E est en outre insensible aux variations de température et d’hygrométrie et son coefficient de dilatation est peu élevé. E-glass fiber thus has a low thermal conductivity. The fiber can withstand temperatures of over 600°C and is non-combustible. In addition, it has excellent chemical resistance. E-glass fibrous products are resistant to oils, solvents, and most chemical agents. In addition, they are rot-proof. The E-glass yarn is also insensitive to variations in temperature and humidity and its coefficient of expansion is low.
Les produits à base de fibre de verre E sont en outre particulièrement résistants à l’abrasion et aux vibrations, et possèdent une excellente flexibilité. Le fil de verre a une résistance spécifique supérieure (résistance traction/ masse volumétrique) à celle de l’acier. Cette caractéristique permet de développer aujourd’hui des fils de verre qui renforceront des composites hautes performances. Habituellement, le verre E est obtenu par fusion d’un bain de matière première comprenant de la silice, de la chaux, du kaolin, une source de bore comme le borax ou l’acide borique et éventuellement de la dolomie, les composants de base étant judicieusement choisis pour fournir une composition de verre produisant des fibres alliant souplesse et robustesse à la traction mécanique
comme à la chaleur, aux agents chimiques comme au potentiel électrique. Pour obtenir les meilleures propriétés, il est indispensable de limiter autant que possible les taux de MgO et d’oxydes d’alcalins Na20 et K2O ou encore d’oxyde de fer Fe2C>3 dans la composition du verre E finalement obtenu. Habituellement, à la silice, la chaux, l’alumine ou la source d’alumine, on ajoute un oxyde de bore tel que le borax ou l’acide borique, tandis que l’on exclut tout oxyde alcalin pour obtenir le verre E. Cette composition est chauffée jusqu’à sa fusion. On considère qu’à 1400°C, le liquide est homogène, mais ce n’est qu’à 1500 °C que les dernières bulles et impuretés disparaissent du verre. Affinée, la masse en fusion est normalement parfaitement transparente à la sortie du four. Cette masse traverse des filières (plaques d’alliages de platine percées de centaines de trous) pour produire un fil de verre. Ce fil est ensuite ensimé, bobiné puis séché. E-glass fiber products are also particularly resistant to abrasion and vibrations, and have excellent flexibility. Glass yarn has a higher specific strength (tensile strength/density) than steel. This characteristic makes it possible today to develop glass yarns that will reinforce high-performance composites. Usually, E-glass is obtained by melting a bath of raw material comprising silica, lime, kaolin, a source of boron such as borax or boric acid and possibly dolomite, the basic components being judiciously chosen to provide a glass composition producing fibers which combine flexibility and strength under mechanical traction as to heat, to chemical agents as to electric potential. To obtain the best properties, it is essential to limit as much as possible the levels of MgO and alkaline oxides Na20 and K2O or even iron oxide Fe2C>3 in the composition of the E glass finally obtained. Usually, to the silica, lime, alumina or alumina source, a boron oxide such as borax or boric acid is added, while any alkali oxide is excluded to obtain E-glass. This composition is heated until it melts. It is considered that at 1400°C, the liquid is homogeneous, but it is only at 1500°C that the last bubbles and impurities disappear from the glass. Refined, the molten mass is normally perfectly transparent when it comes out of the oven. This mass passes through dies (platinum alloy plates pierced with hundreds of holes) to produce a glass thread. This yarn is then sized, wound and then dried.
Il est généralement admis que le choix des matières premières précédemment citées est nécessaire pour obtenir une bonne qualité de verre notamment après son fibrage. Parmi les propriétés jugées comme essentielles, on peut citer notamment le rendement de la fusion (ratio entre la quantité de verre produite et la quantité de matières premières enfournée), la qualité de l’affinage qui se traduit par un nombre minime de bulles résiduelles dans le verre, l’homogénéité du verre (notamment l’homogénéité en S1O2), ainsi que le nombre d’infondus. La consommation énergétique (énergie nécessaire à la fusion du mélange de matières première) peut également être un élément à prendre en compte. It is generally accepted that the choice of the raw materials mentioned above is necessary to obtain a good quality of glass, in particular after its fiber drawing. Among the properties judged to be essential, mention may be made in particular of the yield of the melting (ratio between the quantity of glass produced and the quantity of raw materials charged), the quality of the refining which results in a minimal number of residual bubbles in the glass, the homogeneity of the glass (in particular the homogeneity in S1O2), as well as the number of unmelted particles. The energy consumption (energy required to melt the mixture of raw materials) can also be an element to be taken into account.
Pour répondre aux requis précédents, le verre est habituellement préparé par la fusion dans un four de matières premières comprenant de la silice et au moins un alcalino-terreux (pour donner au verre de la résistance à l’hydrolyse) sous la forme de calcaire (carbonate de calcium). Un porteur d’alumine (tel que le kaolin) et un porteur de bore (par exemple du borax ou de l’acide borique), sont les deux autres éléments majeurs de la composition d’un bain actuel. To meet the above requirements, glass is usually prepared by melting in a furnace raw materials comprising silica and at least one alkaline earth (to give the glass resistance to hydrolysis) in the form of limestone ( calcium carbonate). An alumina carrier (such as kaolin) and a boron carrier (for example borax or boric acid), are the two other major elements in the composition of a current bath.
Parmi les matières premières habituellement utilisées comme source de bore, les plus courantes sont l’acide borique ou le borax comme décrit dans la demande EP1886978A1. L’utilisation du borax qui contient une forte proportion de sodium est cependant limitée afin de maintenir une faible conductivité électrique et l’utilisation d’acide borique, classé comme produit à risque CMR, pose des problèmes de sécurité pour une utilisation à l’échelle industrielle.
L’utilisation de source alternative de bore en remplacement d’au moins une partie du borax ou de l’acide borique, en particulier par une source minérale naturelle, est aussi un des objectifs de la présente invention. Among the raw materials usually used as a source of boron, the most common are boric acid or borax as described in application EP1886978A1. The use of borax, which contains a high proportion of sodium, is however limited in order to maintain low electrical conductivity and the use of boric acid, classified as a CMR risk product, poses safety problems for use on a large scale. industrial. The use of an alternative boron source as a replacement for at least part of the borax or boric acid, in particular with a natural mineral source, is also one of the objectives of the present invention.
Au cours de la fusion, le ou les carbonates dégagent du gaz carbonique dont les bulles contribuent au brassage de la masse en cours de fusion. L’élimination des bulles dans le verre peut également nécessiter l’ajout d’un agent affinant comme le sulfate de sodium ou de calcium dont le dégagement d’oxyde de soufre entraîne vers la surface du verre les bulles résiduelles de gaz carbonique et d’eau. Dans un procédé classique de fabrication du verre pour l’obtention de fibres E, l’émission de CO2 due seulement aux matières premières (sans compter les émissions dues au chauffage et à la montée en température jusqu’à la fusion) est généralement de l’ordre de 15 à 20% de la masse totale des matières premières utilisées. Le gaz carbonique est un gaz à effet de serre et il est souhaitable de mettre au point des procédés de fabrication du verre générant le moins de CO2 possible pour des raisons environnementales, tout en menant à un verre de bonne qualité et pour un coût acceptable. During the melting, the carbonate(s) give off carbon dioxide, the bubbles of which contribute to the mixing of the mass being melted. The elimination of bubbles in the glass may also require the addition of a refining agent such as sodium or calcium sulphate, the release of sulfur oxide from which brings the residual bubbles of carbon dioxide and carbon dioxide to the surface of the glass. water. In a conventional glass manufacturing process for obtaining E fibres, the CO2 emission due only to the raw materials (not counting the emissions due to heating and the rise in temperature until melting) is generally l 15 to 20% of the total mass of raw materials used. Carbon dioxide is a greenhouse gas and it is desirable to develop glass manufacturing processes that generate as little CO2 as possible for environmental reasons, while leading to good quality glass at an acceptable cost.
En plus du dégagement de CO2 directement lors du procédé de fusion du bain de matières premières, il est donc important de considérer le procédé de fabrication du verre E dans sa globalité, en tenant compte d’autres facteurs comme le transport des matières premières ou encore le coût énergétique de la mise à disposition desdites matières premières en vue de leur utilisation dans le procédé de fabrication du verre. Dans un tel but, l’utilisation de matières premières minérales non transformées, à la place des matières débarrassées de leurs impuretés telles qu’actuellement utilisées, présente l’avantage de contribuer à la réduction des émissions de CO2 puisqu’aucune autre énergie de transformation que l’étape de fusion n’entre dans le bilan global de ladite fabrication. In addition to the release of CO2 directly during the melting process of the bath of raw materials, it is therefore important to consider the E-glass manufacturing process as a whole, taking into account other factors such as the transport of raw materials or even the energy cost of making said raw materials available for use in the glass manufacturing process. For such a purpose, the use of unprocessed mineral raw materials, instead of materials stripped of their impurities as currently used, has the advantage of contributing to the reduction of CO2 emissions since no other transformation energy that the melting step enters into the overall balance of said manufacture.
En résumé, dans un objectif de réduire les coûts énergétiques et optimiser le bilan CO2, il est important de tenir compte de l’ensemble des étapes aboutissant à la formation du verre et à la préparation des matières premières en plus de l’étape finale de fusion du bain de matières premières. In summary, with the aim of reducing energy costs and optimizing the CO2 balance, it is important to take into account all the steps leading to the formation of the glass and the preparation of the raw materials in addition to the final step of fusion of the pool of raw materials.
L’objet de la présente invention est de contribuer à résoudre un tel problème technique en proposant un procédé de fabrication du verre E pour lequel les
émissions de CO2 sont effectivement diminuées, sur la base de l’ensemble des étapes aboutissant à la formation de la fibre de verre et pour lequel les étapes de transformation de matière avant la fusion du bain ont été optimisées. The object of the present invention is to contribute to solving such a technical problem by proposing a process for the manufacture of E-glass for which the CO2 emissions are effectively reduced, based on all the steps leading to the formation of the glass fiber and for which the material transformation steps before the melting of the bath have been optimized.
Plus précisément, la présente invention concerne un procédé de fabrication de fibre de verre E présentant une composition cible, comprenant la fusion d’un mélange de matières premières constituant un bain de fusion, ladite composition cible répondant aux critères suivants, en pourcentages poids : More specifically, the present invention relates to a process for manufacturing E-glass fiber having a target composition, comprising the fusion of a mixture of raw materials constituting a fusion bath, said target composition meeting the following criteria, in weight percentages:
- S1O2 : entre 45 et 60%, de préférence entre 50 et 60% - S1O2: between 45 and 60%, preferably between 50 and 60%
- CaO: entre 20 et 35%, de préférence entre 20 et 30% - AI2O3 : entre 10 et 20%, de préférence entre 12 et 18% - CaO: between 20 and 35%, preferably between 20 and 30% - Al2O3: between 10 and 20%, preferably between 12 and 18%
- B2O3 : entre 3 et 10%, de préférence entre 4 et 8% - B2O3: between 3 and 10%, preferably between 4 and 8%
- MgO : moins de 2%, de préférence entre 0 et 1 % - MgO: less than 2%, preferably between 0 and 1%
- K2O + Na20: moins de 2%, de préférence entre 0 et 1 - K2O + Na20: less than 2%, preferably between 0 and 1
- Oxyde de fer : moins de 0,5%, - autre (s) oxyde (s) : entre 0 et 3 % en cumulé, le reste étant constitué d’impuretés inévitables, ledit procédé étant caractérisé en ce qu’il comprend les étapes suivantes : a) on sélectionne les matières premières dudit bain de fusion dont au moins: - une source de silicium notamment choisie parmi la silice, le calcin de verre E ou des fibres minérales recyclées ou leur mélange, de préférence la silice, une source de bore de préférence choisie parmi le borax ou un oxyde de bore et de calcium, en particulier la colémanite, ou un oxyde de bore, de sodium et de calcium, en particulier l’ulexite et/ou un oxyde de bore et de sodium comme la tincalconite et/ou la kernite, ou leurs mélanges, en particulier la colémanite représente au moins 70% poids, de préférence au moins 80% poids de l’ensemble des sources de bore, de préférence encore un mélange de borax et de colémanite. au moins une source de calcium choisie parmi un oxyde mixte de calcium avec au moins un élément choisi dans le groupe constitué
par Si, Al, en particulier un silicate de calcium et/ou un silicate d’aluminium et de calcium, optionnellement une source complémentaire d’aluminium tel que le kaolin, de l’alumine éventuellement hydratée ou la pyrophyllite, optionnellement du calcaire CaCC>3 ou de l’hydroxyde de calcium Ca(OH)2 ou de la chaux vive CaO, la ou lesdites sources de calcium étant des matières minérales naturelles, c’est à dire issue d’un milieu géologique naturel et non transformées, b) on détermine la composition de la ou desdites sources de calcium naturelles, c) sur la base de la ou lesdites compositions déterminées selon le point b), on détermine les quantités nécessaires en lesdites matières premières pour obtenir un verre de ladite composition cible, d) on effectue le mélange desdites matières selon lesdites quantités, e) on effectue la fusion, le fibrage dudit mélange et son refroidissement dans les conditions permettant l’obtention desdites fibres de verre. - Iron oxide: less than 0.5%, - other oxide(s): between 0 and 3% cumulatively, the remainder being made up of unavoidable impurities, said process being characterized in that it comprises the following steps: a) the raw materials of said fusion bath are selected, including at least: - a source of silicon chosen in particular from silica, E-glass cullet or recycled mineral fibers or their mixture, preferably silica, a source boron preferably chosen from borax or a boron and calcium oxide, in particular colemanite, or a boron, sodium and calcium oxide, in particular ulexite and/or a boron and sodium oxide such as tincalconite and/or kernite, or mixtures thereof, in particular colemanite represents at least 70% by weight, preferably at least 80% by weight of all the sources of boron, more preferably a mixture of borax and colemanite. at least one source of calcium selected from a mixed oxide of calcium with at least one element selected from the group consisting by Si, Al, in particular a calcium silicate and/or a calcium aluminum silicate, optionally an additional source of aluminum such as kaolin, optionally hydrated alumina or pyrophyllite, optionally limestone CaCC> 3 or calcium hydroxide Ca(OH)2 or quicklime CaO, said calcium source(s) being natural mineral matter, that is to say coming from a natural geological environment and unprocessed, b) the composition of said natural calcium source(s) is determined, c) on the basis of said composition(s) determined according to point b), the quantities of said raw materials necessary to obtain a glass of said target composition are determined, d) the said materials are mixed according to the said quantities, e) the melting, the fiber drawing of the said mixture and its cooling are carried out under the conditions allowing the production of the said glass fibres.
Selon des modes de réalisations préférés mais non limitatifs de la présente invention, non limitatifs mais qui peuvent bien entendu être combinés entre eux : According to preferred but non-limiting embodiments of the present invention, non-limiting but which can of course be combined with each other:
- Ladite source de calcium est un silicate de calcium minéral naturel comprenant, en pourcentage poids, au moins 30% de S1O2 et au moins 30% poids de CaO, S1O2 et CaO représentant ensemble plus de 70% et de préférence plus de 75% ou même plus de 80% dudit silicate de calcium. - Said source of calcium is a natural mineral calcium silicate comprising, by weight percentage, at least 30% by weight of S1O2 and at least 30% by weight of CaO, S1O2 and CaO together representing more than 70% and preferably more than 75% or even more than 80% of said calcium silicate.
- Ladite source de calcium est une matière minérale naturelle répondant à la composition suivante, en pourcentages poids : - Said source of calcium is a natural mineral material having the following composition, in percentages by weight:
- S1O2 : entre 30 et 55%, de préférence entre 35 et 52%, - S1O2: between 30 and 55%, preferably between 35 and 52%,
- CaO : entre 35 et 50%, de préférence entre 40 et 50%, - CaO: between 35 and 50%, preferably between 40 and 50%,
- CaO et S1O2 représentant ensemble plus de 80%, de préférence encore plus de 85%, - CaO and S1O2 representing together more than 80%, preferably even more than 85%,
- Fe203 : entre 0 et 4%, par exemple entre 0,1 et 0,5% - Fe203: between 0 and 4%, for example between 0.1 and 0.5%
- AI2O3 : entre 0 et 5%, par exemple entre 0,5 et 2% - AI2O3: between 0 and 5%, for example between 0.5 and 2%
- CO2 : entre 0 et 20%, par exemple entre 0 et 15%
- moins de 5% d’autres oxydes, de préférence moins de 3% d’autres oxydes. - CO2: between 0 and 20%, for example between 0 and 15% - less than 5% of other oxides, preferably less than 3% of other oxides.
- Ladite source de calcium est un silicate de calcium et d’aluminium minéral naturel comprenant, en pourcentage poids, plus de 30% de S1O2, plus de 15% poids de CaO et plus de 20% d’ALCb, S1O2, CaO et- Said source of calcium is a natural mineral calcium aluminum silicate comprising, in weight percentage, more than 30% by weight of S1O2, more than 15% by weight of CaO and more than 20% of ALCb, S1O2, CaO and
AI2O3 représentant ensemble plus de 70% et de préférence plus de 75% ou même plus de 80% dudit silicate de calcium. Al2O3 together representing more than 70% and preferably more than 75% or even more than 80% of said calcium silicate.
- Ladite source de calcium est une matière minérale naturelle répondant à la composition suivante, en pourcentages poids : - S1O2 : entre 40 et 60%, de préférence entre 45 et 55%, - Said source of calcium is a natural mineral material having the following composition, in weight percentages: - S1O2: between 40 and 60%, preferably between 45 and 55%,
- CaO : entre 10 et 30%, de préférence entre 12 et 20%, - CaO: between 10 and 30%, preferably between 12 and 20%,
- AI2O3 : entre 25 et 35%, - AI2O3: between 25 and 35%,
- S1O2, CaO et AI2O3 représentant ensemble plus de 85%, de préférence encore plus de 90%, voire plus de 95%, - Na20 : entre 0 et 4%, - S1O2, CaO and Al2O3 together representing more than 85%, preferably even more than 90%, or even more than 95%, - Na20: between 0 and 4%,
- Fe203 : entre 0 et 4%, par exemple entre 0,1 et 1 %, - Fe203: between 0 and 4%, for example between 0.1 and 1%,
- moins de 5% d’autres oxydes, de préférence moins de 3% d’autres oxydes. - less than 5% of other oxides, preferably less than 3% of other oxides.
- On utilise comme matières premières dudit bain de fusion une première source de calcium telle que décrite précédemment et une deuxième source de calcium telle que décrite précédemment. - Is used as raw materials of said melt a first source of calcium as described above and a second source of calcium as described above.
- Ladite source de bore comprend et de préférence est essentiellement, voire est constituée par un oxyde de bore et de calcium comprenant, en pourcentage poids, plus de 30% de B2O3 et plus de 20% poids de CaO. - Said source of boron comprises and preferably consists essentially, or even consists of a boron and calcium oxide comprising, in percentage by weight, more than 30% of B2O3 and more than 20% by weight of CaO.
- La source de bore est constituée majoritairement par un oxyde de bore et de calcium et en particulier par la colémanite. Par majoritairement, on entend en particulier que ledit oxyde de bore et de calcium, en particulier la colémanite, représente plus de 80%, de préférence plus de 85 % voire plus de 90% du poids total de la source de bore. Selon un mode particulier on utilise comme source de bore uniquement ledit un oxyde de bore et de calcium. Selon un autre mode on peut utiliser un mélange d’un oxyde de bore et de calcium tel que la colémanite
avec du borax, dans lequel ledit oxyde de bore et de calcium est majoritaire, en particulier dont le ratio massique borax/ oxyde de bore et de calcium est inférieur à 0,2, voire inférieur à 0,1. - The source of boron consists mainly of an oxide of boron and calcium and in particular colemanite. By predominantly, it is meant in particular that said boron and calcium oxide, in particular colemanite, represents more than 80%, preferably more than 85% or even more than 90% of the total weight of the boron source. According to a particular embodiment, only said one oxide of boron and calcium is used as source of boron. According to another mode, a mixture of an oxide of boron and calcium such as colemanite can be used. with borax, in which said boron and calcium oxide predominates, in particular the borax/boron and calcium oxide mass ratio of which is less than 0.2, or even less than 0.1.
- Ledit oxyde de bore et de calcium, en particulier la colémanite, introduite dans le bain représente plus de 90% poids de l’oxyde de bore- Said boron and calcium oxide, in particular colemanite, introduced into the bath represents more than 90% by weight of the boron oxide
B2O3 contenu dans le verre final. B2O3 contained in the final glass.
- Une source de calcium est un silicate d’aluminium et de calcium.- A source of calcium is calcium aluminum silicate.
- Une source de calcium est constituée par un silicate d’aluminium et de calcium. - La source de calcium comprend un mélange d’un silicate d’aluminium et de calcium et d’un silicate de calcium. - A source of calcium is constituted by a silicate of aluminum and calcium. - The calcium source comprises a mixture of a calcium aluminum silicate and a calcium silicate.
- La source de calcium est constituée par un mélange de silicate d’aluminium et de calcium et d’un silicate de calcium. - The source of calcium is a mixture of aluminum and calcium silicate and a calcium silicate.
- La source de bore comprend la colémanite et la source de calcium comprend un silicate d’aluminium et de calcium. - Boron source includes colemanite and calcium source includes calcium aluminum silicate.
- Une source de bore est un oxyde de bore et de calcium, en particulier la colémanite et la source de calcium comprend et de préférence est constitué par un silicate d’aluminium et de calcium et un silicate de calcium. - La source de bore est constituée majoritairement par ou est constituée par la colémanite et la source de calcium est constituée par un mélange de silicate d’aluminium et de calcium et un silicate de calcium tel que précédemment décrit. - A source of boron is an oxide of boron and calcium, in particular colemanite, and the source of calcium comprises and preferably consists of an aluminum and calcium silicate and a calcium silicate. - The source of boron consists mainly of or consists of colemanite and the source of calcium consists of a mixture of aluminum and calcium silicate and a calcium silicate as previously described.
- Ledit bain comprend un silicate de calcium, un silicate d’aluminium et de calcium et une source de bore constituée par un oxyde de bore et de calcium, en particulier la colémanite. - Said bath comprises a calcium silicate, an aluminum and calcium silicate and a source of boron consisting of a boron and calcium oxide, in particular colemanite.
- L’ensemble des silicates présents dans le bain représente plus de 30% du poids total dudit bain, de préférence plus de 35%, voire plus 40% ou même plus de 45% du poids total dudit bain, voire même plus de 50% du poids total dudit bain. - All the silicates present in the bath represent more than 30% of the total weight of said bath, preferably more than 35%, or even more than 40% or even more than 45% of the total weight of said bath, or even more than 50% of the total weight of said bath.
- On utilise du kaolin ou de la pyrophyllite comme source d’aluminium.
- Le mélange de matières premières contient moins de 12% poids de CO2, de préférence moins de 10% de CO2, de préférence encore moins de 5% de CO2. - Kaolin or pyrophyllite is used as a source of aluminium. - The mixture of raw materials contains less than 12% by weight of CO2, preferably less than 10% of CO2, even more preferably less than 5% of CO2.
- On introduit en outre dans le bain de fusion du calcin de verre E ou des fibres minérales recyclés, en particulier de la laine de verre recyclée ou de la laine de roche recyclée, le calcin de verre E recyclé ou de fibres minérales recyclées représentant de préférence entre 10 et 50% du poids total du bain de fusion. - In addition, recycled E-glass cullet or mineral fibers, in particular recycled glass wool or recycled rock wool, are introduced into the molten pool, the recycled E-glass cullet or recycled mineral fibers representing preferably between 10 and 50% of the total weight of the melt.
Les fibres minérales recyclées présentent la composition suivante : S1O2 : entre 30 et 50%, de préférence entre 35 et 45%,The recycled mineral fibers have the following composition: S1O2: between 30 and 50%, preferably between 35 and 45%,
Na20: entre 0 et 10%, de préférence entre 0,4 et 7%,Na20: between 0 and 10%, preferably between 0.4 and 7%,
CaO: entre 10 et 35%, de préférence entre 12 et 25%,CaO: between 10 and 35%, preferably between 12 and 25%,
MgO : entre 1 et 15%, de préférence entre 5 et 13%,MgO: between 1 and 15%, preferably between 5 and 13%,
CaO+MgO : entre 11 et 40% en cumulé, CaO+MgO: between 11 and 40% cumulatively,
AI2O3 : entre 10 et 27%, AI2O3: between 10 and 27%,
K2O : entre 0 et 2%, de préférence entre 0 et 1 %, K2O: between 0 and 2%, preferably between 0 and 1%,
Oxyde de fer : entre 0,1 et 3%, autre (s) oxyde (s) : entre 0 et 5 % en cumulé, de préférence moins de 3%, le reste étant constitué d’impuretés inévitables. Iron oxide: between 0.1 and 3%, other oxide(s): between 0 and 5% cumulatively, preferably less than 3%, the remainder being made up of unavoidable impurities.
L’invention concerne également le mélange de matières premières décrit précédemment. The invention also relates to the mixture of raw materials described above.
De préférence encore, les matières premières sont sélectionnées de telle manière que dans la composition finale du verre E selon l’invention : Preferably again, the raw materials are selected in such a way that in the final composition of the E-glass according to the invention:
- le rapport massique B203/(Na20+K20) est compris entre 5 et 15, de préférence encore est compris entre 6 et 10. - the B203/(Na20+K20) mass ratio is between 5 and 15, more preferably is between 6 and 10.
- le rapport massique B203/(Na20+K20+Mg0) est compris entre 4,0 et 8,0. Avantageusement, une faible teneur en alcalins permet de ne pas dégrader les performances diélectriques du verre à teneur de bore constant et une faible teneur en magnésium permet de ne pas monter la température du liquidus du verre.
Le mélange de matières premières selon l’invention est destiné à être chauffé à une température et dans des conditions permettant sa fusion pour l’obtention d’un verre répondant à ladite composition cible. - the B203/(Na20+K20+Mg0) mass ratio is between 4.0 and 8.0. Advantageously, a low alkali content makes it possible not to degrade the dielectric performance of the glass with a constant boron content and a low magnesium content makes it possible not to raise the temperature of the liquidus of the glass. The mixture of raw materials according to the invention is intended to be heated to a temperature and under conditions allowing its melting in order to obtain a glass corresponding to said target composition.
L’originalité de la présente invention réside dans le choix des matières premières. En effet, il a été découvert qu’il était possible d’utiliser des oxydes minéraux naturels, c’est dire sous leur composition initiale géologique après leur extraction de leur gisement, y compris leurs éventuelles impuretés, en particulier sans altération chimique visant à en modifier la composition initiale, c'est-à-dire des matières minérales non transformées chimiquement, comme source de calcium et éventuellement d’aluminium, ce choix conduisant avantageusement à la diminution du dégagement de CO2 lors de la réaction de fusion. En particulier, selon le procédé de la présente invention, on se base initialement sur la composition exacte de ces matières minérales géologiques non transformées, telle que déterminée précisément par toute technique adéquate (par exemple analyse chimique, diffraction des rayons X, etc.) pour déterminer la composition du bain initial. Plus précisément, sur la base de cette détermination initiale de la composition de la matière minérale, on calcule les proportions nécessaires en les autres composants dudit bain pour arriver à une composition cible du verre final, de manière à minimiser la quantité de CO2 dégagée, telle que mesurée sur l’ensemble des étapes conduisant à la formation du verre, et pas uniquement sur la base de l’étape finale de fusion. The originality of the present invention lies in the choice of raw materials. Indeed, it was discovered that it was possible to use natural mineral oxides, that is to say under their initial geological composition after their extraction from their deposit, including their possible impurities, in particular without chemical alteration aimed at modifying the initial composition, that is to say mineral materials not chemically transformed, as a source of calcium and possibly of aluminium, this choice advantageously leading to a reduction in the release of CO2 during the fusion reaction. In particular, according to the process of the present invention, the basis is initially based on the exact composition of these untransformed geological mineral materials, as determined precisely by any suitable technique (for example chemical analysis, X-ray diffraction, etc.) for determine the composition of the initial bath. More specifically, on the basis of this initial determination of the composition of the mineral matter, the necessary proportions of the other components of said bath are calculated to arrive at a target composition of the final glass, so as to minimize the quantity of CO2 released, such as than measured on all the steps leading to the formation of the glass, and not only on the basis of the final melting step.
Selon l’invention cependant lesdits oxydes minéraux peuvent bien entendu subir des étapes préalables à leur utilisation comme matière première de la fusion, mais sans transformation chimique, comme un concassage, un criblage, une séparation magnétique, un lavage ou encore une flottation ou toute autre séparation physique, pourvu qu’elle ne change pas ou sensiblement pas la composition chimique du composé minéral initial. According to the invention, however, said mineral oxides can of course undergo steps prior to their use as raw material for fusion, but without chemical transformation, such as crushing, screening, magnetic separation, washing or even flotation or any other physical separation, provided that it does not or substantially change the chemical composition of the initial mineral compound.
Avec un tel mélange, il est possible de réduire sensiblement voire d’annuler les émissions de CO2 provenant des matières premières, non seulement durant l’étape de fusion mais également de réduire sensiblement celles-ci dans les étapes préalables.
Comme démontré dans les exemples qui suivent, on a ainsi pu obtenir des fibres de verre E sans défauts à partir du mélange initial selon l’invention comme il sera montré dans les exemples qui suivent. With such a mixture, it is possible to substantially reduce or even eliminate the CO2 emissions originating from the raw materials, not only during the melting stage but also to substantially reduce them in the preliminary stages. As demonstrated in the examples which follow, it was thus possible to obtain E-glass fibers without defects from the initial mixture according to the invention as will be shown in the examples which follow.
Selon l’invention, on introduit le moins possible de carbonate, voire aucun carbonate dans le mélange de matières premières. De préférence, la somme du poids de carbonate(s) est inférieure à 20%, et de préférence inférieure à 10%, et de préférence inférieure à 5%, et de préférence inférieure à 1% en poids, voire est nulle dans le mélange de matières premières. Selon un mode possible avantageux, le mélange de matières premières est exempt de tout carbonate. Il est avantageusement apte à ne dégager sensiblement aucun oxyde de carbone lors de son chauffage et sa fusion en verre, par exemple moins de 2% ou moins de 1 %. According to the invention, as little carbonate as possible, or even no carbonate, is introduced into the mixture of raw materials. Preferably, the sum of the weight of carbonate(s) is less than 20%, and preferably less than 10%, and preferably less than 5%, and preferably less than 1% by weight, or even zero in the mixture of raw materials. According to one possible advantageous mode, the mixture of raw materials is free of any carbonate. It is advantageously capable of giving off substantially no carbon monoxide during its heating and its melting into glass, for example less than 2% or less than 1%.
Pour réaliser le verre, le porteur de Si est très préférentiellement introduit dans le mélange de matières premières sous forme de sable. Le porteur de calcium est apporté sous la forme d’un silicate de calcium et/ou d’un silicate de calcium et d’aluminium. Le porteur d’AI peut avantageusement être introduit dans le mélange de matières premières sous forme d’un silicate de calcium et d’aluminium, identique ou différent du précédent. Chaque matière première est introduite dans le mélange de matières premières en quantité telle que le pourcentage molaire de son cation (comme Si, Ca, Al, B, etc.) par rapport à la somme des moles de tous les cations soit le même que dans le verre final. Les matières premières du mélange sont choisies pour mener à un verre dont la composition cible entre dans le cadre (les gammes de pourcentage en les différents oxydes) décrit(es) précédemment. Le mélange de matières premières est chauffé jusqu’à l’obtention d’un verre fondu, généralement dans un four. On chauffe plus ou moins haut en température et plus ou moins longtemps selon la qualité du verre que l’on cherche, notamment selon le degré de tolérance en particules non fondues (appelées « infondus ») et en bulles. Généralement, la température maximale de chauffage du verre fondu est comprise entre 1400 et 1700°C. Pour la transformation du mélange de matières premières en verre, on peut faire appel aux techniques de fusion du verre bien connues de l’homme du métier. Cette transformation peut être réalisée dans tout type de four comme un four électrique
à électrodes, un four à brûleurs aériens comme un four à brûleurs transversaux ou un four à boucle, un four à brûleurs immergés. To produce the glass, the Si carrier is very preferably introduced into the mixture of raw materials in the form of sand. The calcium carrier is provided in the form of a calcium silicate and/or a calcium aluminum silicate. The Al carrier can advantageously be introduced into the mixture of raw materials in the form of a calcium and aluminum silicate, identical to or different from the previous one. Each feedstock is introduced into the feedstock mixture in an amount such that the mole percentage of its cation (such as Si, Ca, Al, B, etc.) relative to the sum of moles of all cations is the same as in the final drink. The raw materials of the mixture are chosen to lead to a glass whose target composition falls within the scope (the percentage ranges of the different oxides) described above. The mixture of raw materials is heated until a molten glass is obtained, usually in a furnace. The temperature is heated more or less high and for more or less time depending on the quality of the glass you are looking for, in particular according to the degree of tolerance of unmelted particles (called "unmelted") and bubbles. Generally, the maximum heating temperature of molten glass is between 1400 and 1700°C. For the transformation of the mixture of raw materials into glass, use may be made of glass melting techniques well known to those skilled in the art. This transformation can be carried out in any type of oven such as an electric oven with electrodes, a furnace with overhead burners such as a furnace with transverse burners or a loop furnace, a furnace with submerged burners.
Le mélange de matières premières, notamment pulvérulent, peut éventuellement être humidifié avant introduction dans un four afin de réduire les envols de matières premières dans le four en raison des courants de gaz de combustion. Pour le chauffage et la fusion en verre, le mélange de matières premières, le cas échéant humidifié, peut être introduit dans un four à l’état pulvérulent, ce qui implique que chaque matière première qu’il contient est à l’état de poudre. Pour le chauffage et la fusion en verre, le mélange de matières premières, le cas échéant humidifié, peut être introduit dans un four à l’état de composition comprenant du calcin et le mélange de matières premières, ce dernier étant le cas échéant pulvérulent. The mixture of raw materials, in particular pulverulent, can possibly be humidified before introduction into a furnace in order to reduce the flights of raw materials in the furnace due to the currents of combustion gases. For heating and melting glass, the mixture of raw materials, if necessary humidified, can be introduced into a furnace in a powder state, which implies that each raw material it contains is in a powder state. . For heating and glass melting, the mixture of raw materials, moistened if necessary, can be introduced into a furnace in the state of composition comprising cullet and the mixture of raw materials, the latter being powdery if necessary.
Dans le cadre de la présente invention, on peut s’affranchir de l’utilisation d’un système de conformation (c’est-à-dire de mise en forme) du mélange de matières premières par pression mécanique, notamment utilisant des moules menant à des agglomérats calibrées (briquettes, boulets, granulés, pellets, etc), comme des compacteuses à frettes. Ainsi, avant introduction dans un four, le mélange de matières premières peut ne pas être conformé par pression mécanique. Il n’est pas non plus nécessaire d’utiliser une technique de granulation de la matière première selon laquelle la matière est mise en rotation (notamment dans une cuve du type tambour en rotation) généralement en présence d’un liant de façon à mener à des granulés (pellets en anglais). In the context of the present invention, it is possible to dispense with the use of a system for conforming (that is to say shaping) the mixture of raw materials by mechanical pressure, in particular using molds leading to calibrated agglomerates (briquettes, balls, granules, pellets, etc.), such as fret compactors. Thus, before introduction into a furnace, the mixture of raw materials may not be shaped by mechanical pressure. It is also not necessary to use a technique for granulating the raw material according to which the material is put into rotation (in particular in a tank of the rotating drum type) generally in the presence of a binder so as to lead to pellets.
Exemples Selon cette série d’exemples, on prépare différents mélanges de matière premières afin de comparer un mélange tel qu’actuellement utilisé pour la fabrication verre E pour l’obtention finale d’une même composition, laquelle a sensiblement la formulation suivante en pourcentage poids d’oxydes : Examples According to this series of examples, different mixtures of raw materials are prepared in order to compare a mixture as currently used for the manufacture of E glass for the final obtaining of the same composition, which has substantially the following formulation in weight percentage of oxides:
[Table 1]
[Table 1]
Exemple 1 (art antérieur) Example 1 (prior art)
Selon un premier exemple on synthétise une composition de la synthèse de verre E répondant à la formulation précédente. Le tableau 2 ci-dessous donne les proportions des différentes matières premières (en pourcentage poids) et la composition finale du verre ainsi obtenu : [Table 2]
According to a first example, a composition of the synthesis of glass E corresponding to the preceding formulation is synthesized. Table 2 below gives the proportions of the different raw materials (in percentage by weight) and the final composition of the glass thus obtained: [Table 2]
Le mélange de matières premières est porté sous air en creuset de platine en 1 h jusqu’à 1400°C puis jusqu’à fusion du verre à 1500°C avec un palier d’une heure à la température maximale. La quantité de CO2 dégagée est de 155 grammes. The mixture of raw materials is brought under air in a platinum crucible in 1 hour up to 1400°C then until the glass melts at 1500°C with a one-hour plateau at the maximum temperature. The amount of CO2 released is 155 grams.
Exemple 2 : Dans cet exemple le mélange de matières premières est cette fois tel que décrit dans le tableau 3 ci-dessous. Example 2: In this example the mixture of raw materials is this time as described in Table 3 below.
Dans ce mélange initial on a introduit comme réactif, pour remplacer le calcaire, une matière minérale naturelle constitué d’un silicate de calcium et d’aluminium naturel issu d’une carrière située à Lapinlahti (Finlande). Cette matière minérale est directement introduite, sans aucune transformation chimique et après un simple broyage visant à en adapter la granulométrie, avec
les autres constituants dans des proportions ajustées en conséquence pour l’obtention d’un verre de composition très proche de celle de l’exemple 1 de référence, et pour minimiser le dégagement de CO2. In this initial mixture was introduced as a reagent, to replace the limestone, a natural mineral material consisting of a silicate of calcium and natural aluminum from a quarry located in Lapinlahti (Finland). This mineral matter is directly introduced, without any chemical transformation and after a simple grinding aiming to adapt the granulometry, with the other constituents in proportions adjusted accordingly to obtain a glass with a composition very close to that of reference Example 1, and to minimize the release of CO2.
[Table 3]
[Table 3]
Comme pour l’exemple 1 , le mélange de matières premières est porté sous air en creuset de platine en 1 h jusqu’à 1400°C puis jusqu’à fusion du verre à 1500°C avec un palier d’une heure à la température maximale. La quantité de CO2 dégagée est cette fois de 94 grammes, soit une diminution de 40% par rapport à l’exemple de référence. As for Example 1, the mixture of raw materials is brought under air in a platinum crucible in 1 hour up to 1400° C. then until the glass melts at 1500° C. with a one-hour plateau at the temperature maximum. The amount of CO2 released this time is 94 grams, a decrease of 40% compared to the reference example.
Exemple 3 : Example 3:
Dans cet exemple le mélange de matières premières est cette fois tel que décrit dans le tableau 4 ci-dessous. Dans ce mélange initial on a introduit comme réactif, pour remplacer le calcaire, une matière minérale naturelle d’un silicate de calcium directement issue d’une carrière située à Sonora. In this example, the mixture of raw materials is this time as described in Table 4 below. In this initial mixture we introduced as a reagent, to replace the limestone, a natural mineral matter of a calcium silicate directly from a quarry located in Sonora.
Cette matière est directement introduite, sans aucune transformation chimique et après un simple broyage visant à en adapter la granulométrie, en mélange avec les autres constituants dans des proportions ajustées en conséquence pour l’obtention d’un verre de composition très proche de celle de l’exemple 1 de référence. This material is introduced directly, without any chemical transformation and after simple grinding aimed at adapting the particle size, mixed with the other constituents in proportions adjusted accordingly to obtain a glass with a composition very close to that of glass. reference example 1.
[Table 4]
[Table 4]
Comme pour l’exemple 1, le mélange de matières premières est porté sous air en creuset de platine en 1 h jusqu’à 1400°C puis jusqu’à fusion du verre à 1500°C avec un palier d’une heure à la température maximale. Aucun dégagement de CO2 n’est observé pour cet exemple. As for Example 1, the mixture of raw materials is brought under air in a platinum crucible in 1 hour up to 1400° C. then until the glass melts at 1500° C. with a one-hour plateau at the temperature maximum. No CO2 release is observed for this example.
Exemple 4 : Example 4:
Dans cet exemple le mélange de matières premières est cette fois tel que décrit dans le tableau 5 ci-dessous. Dans ce mélange initial on a introduit comme réactif, pour remplacer l’ensemble du calcaire, de matières minérales comprenant un mélange du silicate de calcium selon l’exemple 3 et du silicate de calcium et d’aluminium naturel de l’exemple 2. La composition en oxydes de cette matière minérale est donnée ci-après. In this example, the mixture of raw materials is this time as described in Table 5 below. In this initial mixture was introduced as reagent, to replace all the limestone, mineral matter comprising a mixture of calcium silicate according to Example 3 and calcium silicate and natural aluminum of Example 2. composition in oxides of this mineral matter is given below.
[Table 5]
[Table 5]
Comme pour l’exemple 1, le mélange de matières premières est porté sous air en creuset de platine en 1 h jusqu’à 1400°C puis jusqu’à fusion du verre à 1500°C avec un palier d’une heure à la température maximale. Aucun dégagement de CO2 n’est observé pour cet exemple.
Exemple 5 : As for Example 1, the mixture of raw materials is brought under air in a platinum crucible in 1 hour up to 1400° C. then until the glass melts at 1500° C. with a one-hour plateau at the temperature maximum. No release of CO2 is observed for this example. Example 5:
Dans cet exemple le mélange de matières premières est cette fois tel que décrit dans le tableau 6 ci-dessous. In this example, the mixture of raw materials is this time as described in Table 6 below.
Dans ce mélange initial on a introduit comme réactif, pour remplacer l’ensemble du calcaire, de matières minérales comprenant un autre mélange d’un silicate de calcium déjà décrit dans l’exemple 3 et du silicate de calcium et d’aluminium naturel de l’exemple 2. La composition en oxydes de cette matière minérale est donnée ci-après. In this initial mixture was introduced as a reagent, to replace all of the limestone, mineral matter comprising another mixture of a calcium silicate already described in Example 3 and natural calcium and aluminum silicate from l Example 2. The oxide composition of this mineral material is given below.
[Table 6]
[Table 6]
Comme pour l’exemple 1, le mélange de matières premières est porté sous air en creuset de platine en 1 h jusqu’à 1400°C puis jusqu’à fusion du verre à 1500°C avec un palier d’une heure à la température maximale. Aucun dégagement de CO2 n’est observé pour cet exemple. As for Example 1, the mixture of raw materials is brought under air in a platinum crucible in 1 hour up to 1400° C. then until the glass melts at 1500° C. with a one-hour plateau at the temperature maximum. No CO2 release is observed for this example.
Exemple 6 : Example 6:
Dans cet exemple le mélange de matières premières est cette fois tel que décrit dans le tableau 7 ci-dessous. In this example, the mixture of raw materials is this time as described in Table 7 below.
Dans ce mélange initial on a introduit comme réactif, pour remplacer l’ensemble du calcaire, de matières minérales comprenant un mélange du silicate de calcium issu d’une carrière située à Hermosillo et du silicate de calcium et d’aluminium naturel de l’exemple 2. La composition en oxydes de cette matière minérale est donnée ci-après. In this initial mixture was introduced as a reagent, to replace all the limestone, mineral materials comprising a mixture of calcium silicate from a quarry located in Hermosillo and calcium silicate and natural aluminum of the example 2. The oxide composition of this mineral matter is given below.
[Table 7]
[Table 7]
Comme pour l’exemple 1, le mélange de matières premières est porté sous air en creuset de platine en 1 h jusqu’à 1400°C puis jusqu’à fusion du verre à 1500°C avec un palier d’une heure à la température maximale. La quantité de CO2 dégagée est cette fois de 30 grammes, soit une diminution de 81 % par rapport à l’exemple de référence. As for Example 1, the mixture of raw materials is brought under air in a platinum crucible in 1 hour up to 1400° C. then until the glass melts at 1500° C. with a one-hour plateau at the temperature maximum. The amount of CO2 released this time is 30 grams, a decrease of 81% compared to the reference example.
Exemple 7 : Example 7:
Dans cet exemple le mélange de matières premières est cette fois tel que décrit dans le tableau 8 ci-dessous. In this example, the mixture of raw materials is this time as described in Table 8 below.
Dans ce mélange initial on a introduit comme réactif, pour remplacer l’ensemble du calcaire, de matières minérales comprenant un autre mélange d’un silicate de calcium déjà décrit dans l’exemple 6 et du silicate de calcium et d’aluminium naturel de l’exemple 2. La composition en oxydes de cette matière minérale est donnée ci-après. In this initial mixture was introduced as a reagent, to replace all of the limestone, mineral materials comprising another mixture of a calcium silicate already described in Example 6 and natural calcium and aluminum silicate from l Example 2. The oxide composition of this mineral material is given below.
[Table 8]
Comme pour l’exemple 1 , le mélange de matières premières est porté sous air en creuset de platine en 1 h jusqu’à 1400°C puis jusqu’à fusion du verre à 1500°C avec un palier d’une heure à la température maximale. La quantité de CO2 dégagée est cette fois de 44 grammes, soit une diminution de 72% par rapport à l’exemple de référence. [Table 8] As for Example 1, the mixture of raw materials is brought under air in a platinum crucible in 1 hour up to 1400° C. then until the glass melts at 1500° C. with a one-hour plateau at the temperature maximum. The amount of CO2 released this time is 44 grams, a decrease of 72% compared to the reference example.
La qualité du verre E obtenue à partir des bains fondus de verre selon les exemples 1 (comparatif) et 2 à 4 qui précèdent, est donnée dans le tableau 9 ci- dessous, dans lequel on a reporté différents critères obtenus selon les mesures suivantes : The quality of the E glass obtained from the molten baths of glass according to examples 1 (comparative) and 2 to 4 above, is given in table 9 below, in which various criteria obtained according to the following measurements have been reported:
1 °) Rendement 1°) Yield
C’est le rapport entre la quantité de verre produite et la quantité de matières premières enfournée. Plus ce ratio est élevé, plus la quantité de verre pouvant être produit est élevé et plus les émissions de gaz (CO2, H2O) sont faibles.It is the ratio between the quantity of glass produced and the quantity of raw materials loaded. The higher this ratio, the greater the amount of glass that can be produced and the lower the gas emissions (CO2, H2O).
2°) Quantité de sable : c’est la quantité de sable utilisée par rapport à l’exemple 1 de référence (en pourcentage poids économisé). Outre les considérations liées à la silicose, diminuer la quantité de sable utilisée au profit d’autres matières minérales tels que les silicates naturels permet de diminuer l'énergie pour fondre le verre, la matière première la plus réfractaire du bain étant généralement la silice. 2°) Quantity of sand: this is the quantity of sand used compared to reference example 1 (in percentage weight saved). In addition to the considerations linked to silicosis, reducing the quantity of sand used in favor of other mineral materials such as natural silicates makes it possible to reduce the energy to melt the glass, the most refractory raw material in the bath generally being silica.
3°) Qualité de l’affinage (ou taux bulles) : 3°) Quality of refining (or bubble rate):
On mesure le nombre de bulles par kilogramme de verre fondu à 1410°C pendant 240 minutes. Plus cet indice est élevé plus l’affinage est de bonne qualité. The number of bubbles per kilogram of molten glass is measured at 1410° C. for 240 minutes. The higher this index, the better the quality of ripening.
*** : nombre de bulles exemple/nombre de bulles exemple 1 de référence < 100% **** : nombre de bulles exemple/nombre de bulles exemple 1 de référence < 50% 4°) Homogénéité en S1O2 : *** : number of bubbles example/number of bubbles example 1 reference < 100% **** : number of bubbles example/number of bubbles example 1 reference < 50% 4°) Homogeneity in S1O2:
L’indice de qualité est proportionnel à l’homogénéité en S1O2 (telle que mesurée par microsonde/EDS) du verre fondu à 1410°C pendant 240min. The quality index is proportional to the S1O2 homogeneity (as measured by microprobe/EDS) of the molten glass at 1410°C for 240min.
L’homogénéité est mesurée par une série de mesures de la quantité de S1O2 en différents points du verre et un écart type est ensuite déterminé. Homogeneity is measured by a series of measurements of the amount of S1O2 at different points in the glass and a standard deviation is then determined.
* : écart type S1O2 (mesurée par microsonde/EDS) >1 ,0% * : S1O2 standard deviation (measured by microprobe/EDS) >1.0%
** : écart type S1O2 (mesurée par microsonde/EDS) >0,5%
*** : écart type S1O2 (mesurée par microsonde/EDS) compris entre 0,1 et 0,5% **** : écart type Si02 (mesurée par microsonde/EDS) <0,1 % ** : S1O2 standard deviation (measured by microprobe/EDS) >0.5% *** : standard deviation S1O2 (measured by microprobe/EDS) between 0.1 and 0.5% **** : standard deviation Si02 (measured by microprobe/EDS) <0.1%
5°) Nombre de défauts solides (infondus) 5°) Number of solid defects (unmelted)
Cette mesure correspond à la quantité de défauts solides après une fusion à 1250°C arrêtée après 120min. Dans le tableau 9 : This measurement corresponds to the quantity of solid defects after melting at 1250°C stopped after 120min. In Table 9:
- Supérieur indique que le nombre d’infondus est supérieur à la qualité standard (exemple 1 de référence), - Higher indicates that the number of unmelted is higher than the standard quality (example 1 of reference),
- Inférieur indique que le nombre d’infondus est inférieur à la qualité standard (exemple 1 de référence). - Lower indicates that the number of unmelted is lower than the standard quality (reference example 1).
6°) Consommation énergétique : 6°) Energy consumption:
Cette mesure correspond à l’énergie nécessaire à la fusion du mélange de matières première, telle que mesurée par DSC (en pourcentage économisé par rapport à l’exemple 1 de référence) This measurement corresponds to the energy required to melt the mixture of raw materials, as measured by DSC (as a percentage saved compared to the reference example 1)
[Table 91
[Table 91
La comparaison des résultats ci-dessus montre que les exemples 2 à 4 selon l’invention montrent des indices de qualité globalement supérieurs à l’exemple 1 de référence. The comparison of the above results shows that examples 2 to 4 according to the invention show overall higher quality indices than reference example 1.
Tous les exemples selon l’invention montrent qu’il est possible d’utiliser un silicate de calcium naturel et/ou un silicate de calcium et d’aluminium naturel en combinaison avec, comme source de bore, un oxyde de bore et de calcium minéral naturel tel que la colémanite, pour obtenir la composition de verre désirée sans besoin de transformation ou de traitement préalable. All the examples according to the invention show that it is possible to use a natural calcium silicate and/or a natural calcium and aluminum silicate in combination with, as source of boron, a boron oxide and mineral calcium. natural material such as colemanite, to obtain the desired glass composition without the need for transformation or pre-treatment.
L’exemple 2 selon l’invention montre que l’utilisation d’un silicate de calcium et d’aluminium naturel en combinaison avec la colémanite permet d’obtenir un verre
de qualité et surtout présentant un faible degré d’infondus, et même inférieur à la référence, ce qui est essentielle pour son utilisation. Un tel résultat apparaît surprenant, si on regarde le point de fusion de la colémanite (autour de 1100 °C) utilisé en combinaison avec un silicate de calcium et d’aluminium dans le bain de fusion. Example 2 according to the invention shows that the use of a natural calcium and aluminum silicate in combination with colemanite makes it possible to obtain a glass quality and especially with a low degree of unmelted, and even lower than the reference, which is essential for its use. Such a result appears surprising, if we look at the melting point of colemanite (around 1100°C) used in combination with a calcium and aluminum silicate in the melt.
Selon l’exemple 3, l’utilisation d’un silicate de calcium naturel en combinaison avec la colémanite présente des avantages particuliers et en particulier une très forte réduction de la quantité de sable nécessaire, une homogénéité améliorée et un gain énergétique certain mais en contrepartie de la présence d’une quantité plus importantes d’infondus que la référence. According to Example 3, the use of a natural calcium silicate in combination with colemanite has particular advantages and in particular a very strong reduction in the quantity of sand required, improved homogeneity and a certain energy gain but in return the presence of a greater quantity of unmelted particles than the reference.
L’exemple 4 selon l’invention dans lequel on utilise comme matières premières dudit bain de fusion une première source de calcium constitué par un silicate de calcium minéral naturel et une deuxième source de calcium constitué par un silicate de calcium et d’aluminium minéral naturel, en combinaison avec une source de bore essentiellement constituée d’un oxyde de bore et de calcium (tel que la colémanite) apparaît particulièrement avantageux selon tous les critères de qualité listés dans le tableau 9 qui précède. Example 4 according to the invention in which a first source of calcium consisting of a natural mineral calcium silicate and a second source of calcium consisting of a natural mineral calcium and aluminum silicate are used as raw materials of said melt , in combination with a source of boron essentially consisting of a boron oxide and calcium (such as colemanite) appears particularly advantageous according to all the quality criteria listed in Table 9 above.
Le tableau 10 qui suit donne pour les différents exemples les taux de K2O, Na2Ü et MgO des exemples selon l’invention. Table 10 which follows gives for the various examples the contents of K2O, Na2Ü and MgO of the examples according to the invention.
Table 10l
Table 10l
On peut voir que les taux de MgO, Na20, Fe203 et K2O restent extrêmement bas, malgré l’utilisation dans le bain de fusion de matières minérales non transformées. On observe en particulier que les taux de MgO et la somme Na20 + K2O sont compris entre 0 et 1% et un taux de Fe203 inférieur à 0,5% dans la composition du verre final, ce qui permet de garantir en outre une faible résistivité électrique du verre.
It can be seen that the levels of MgO, Na20, Fe203 and K2O remain extremely low, despite the use of unprocessed mineral materials in the melt. It is observed in particular that the MgO levels and the Na20 + K2O sum are between 0 and 1% and an Fe203 level of less than 0.5% in the composition of the final glass, which also makes it possible to guarantee low resistivity. electric glass.
Claims
1. Procédé de fabrication de fibres de verre E présentant une composition cible, comprenant la fusion d’un mélange de matières premières constituant un bain de fusion, ladite composition cible répondant aux critères suivants, en pourcentages poids : 1. Process for manufacturing E-glass fibers having a target composition, comprising the melting of a mixture of raw materials constituting a melt, said target composition meeting the following criteria, in weight percentages:
SiC>2 : entre 45 et 60%, de préférence entre 50 et 60% SiC>2: between 45 and 60%, preferably between 50 and 60%
CaO: entre 20 et 35%, de préférence entre 20 et 30% CaO: between 20 and 35%, preferably between 20 and 30%
AI2O3 : entre 10 et 20%, de préférence entre 12 et 18% AI2O3: between 10 and 20%, preferably between 12 and 18%
B2O3 : entre 3 et 10%, de préférence entre 4 et 8% B2O3: between 3 and 10%, preferably between 4 and 8%
MgO : moins de 2%, de préférence entre 0 et 1 % MgO: less than 2%, preferably between 0 and 1%
K2O + Na20: moins de 2%, de préférence entre 0 et 1% K2O + Na20: less than 2%, preferably between 0 and 1%
Oxyde de fer : moins de 0,5%, autre (s) oxyde (s) : entre 0 et 3 % en cumulé, le reste étant constitué d’impuretés inévitables, ledit procédé étant caractérisé en ce qu’il comprend les étapes suivantes : a) on sélectionne les matières premières dudit bain de fusion dont au moins: Iron oxide: less than 0.5%, other oxide(s): between 0 and 3% cumulatively, the remainder consisting of unavoidable impurities, said method being characterized in that it comprises the following steps : a) the raw materials of said molten pool are selected, including at least:
- une source de silicium notamment choisie parmi la silice, le calcin de verre E ou des fibres minérales recyclées ou leur mélange,- a source of silicon chosen in particular from silica, E-glass cullet or recycled mineral fibers or a mixture thereof,
- une source de bore de préférence choisie parmi le borax ou un oxyde de bore et de calcium, en particulier la colémanite, ou un oxyde de bore, de sodium et de calcium, en particulier l’ulexite et/ou la tincalconite et/ou la kernite, - a source of boron preferably chosen from borax or a boron and calcium oxide, in particular colemanite, or a boron, sodium and calcium oxide, in particular ulexite and/or tincalconite and/or kernitus,
- au moins une source de calcium choisie parmi un oxyde mixte de calcium avec au moins un élément choisi dans le groupe constitué par Si, Al, en particulier un silicate de calcium et/ou un silicate d’aluminium et de calcium, de préférence un silicate d’aluminium et de calcium,- at least one source of calcium chosen from a mixed oxide of calcium with at least one element chosen from the group consisting of Si, Al, in particular a calcium silicate and/or an aluminum and calcium silicate, preferably a aluminum and calcium silicate,
- optionnellement une source d’aluminium tel que le kaolin, de l’alumine éventuellement hydratée ou la pyrophyllite, - optionally a source of aluminum such as kaolin, optionally hydrated alumina or pyrophyllite,
- optionnellement du calcaire CaCOs ou de l’hydroxyde de calcium Ca (OH)2 OU de la chaux vive CaO, la ou lesdites sources de calcium étant des matières minérales naturelles, c’est à dire issue(s) d’un milieu géologique naturel et non transformées,
b) on détermine la composition de la ou desdites sources de calcium naturelles, c) sur la base de la ou lesdites compositions déterminées selon le point b), on détermine les quantités nécessaires en lesdites matières premières pour obtenir un verre de ladite composition cible, d) on effectue le mélange desdites matières selon lesdites quantités, e) on effectue la fusion, le fibrage dudit mélange et son refroidissement dans les conditions permettant l’obtention desdites fibres de verre.- optionally limestone CaCOs or calcium hydroxide Ca (OH) 2 OR quicklime CaO, said source or sources of calcium being natural mineral materials, i.e. resulting from a geological environment natural and unprocessed, b) the composition of said natural calcium source(s) is determined, c) on the basis of said composition(s) determined according to point b), the quantities of said raw materials necessary to obtain a glass of said target composition are determined, d) the said materials are mixed according to the said quantities, e) the melting, the fiber drawing of the said mixture and its cooling are carried out under the conditions allowing the production of the said glass fibers.
2. Procédé selon la revendication précédente, dans lequel une source de calcium est un silicate de calcium minéral naturel comprenant, en pourcentage poids, au moins 30% de S1O2 et au moins 30% poids de CaO, S1O2 et CaO représentant ensemble plus de 70% et de préférence plus de 80% dudit silicate de calcium. 2. Method according to the preceding claim, in which a source of calcium is a natural mineral calcium silicate comprising, in weight percentage, at least 30% of S1O2 and at least 30% by weight of CaO, S1O2 and CaO representing together more than 70 % and preferably more than 80% of said calcium silicate.
3. Procédé selon la revendication précédente dans lequel ladite source de calcium est une matière minérale naturelle répondant à la composition suivante, en pourcentages poids : 3. Method according to the preceding claim, in which said source of calcium is a natural mineral material having the following composition, in percentages by weight:
- S1O2 : entre 30 et 55%, de préférence entre 35 et 52%, - S1O2: between 30 and 55%, preferably between 35 and 52%,
- CaO : entre 35 et 50%, de préférence entre 40 et 50%, - CaO: between 35 and 50%, preferably between 40 and 50%,
- CaO et S1O2 représentant ensemble plus de 80%, de préférence encore plus de 85%, - CaO and S1O2 representing together more than 80%, preferably even more than 85%,
- Fe203 : entre 0 et 4%, par exemple entre 0,1 et 0,5% - Fe203: between 0 and 4%, for example between 0.1 and 0.5%
- AI2O3 : entre 0 et 5%, par exemple entre 0,5 et 2% - AI2O3: between 0 and 5%, for example between 0.5 and 2%
- CO2 : entre 0 et 20%, par exemple entre 0 et 15% - CO2: between 0 and 20%, for example between 0 and 15%
- moins de 5% d’autres oxydes, de préférence moins de 3% d’autres oxydes. - less than 5% of other oxides, preferably less than 3% of other oxides.
4. Procédé selon l’une des revendications précédentes, dans lequel une source de calcium est un silicate de calcium et d’aluminium minéral naturel comprenant, en pourcentage poids, plus de 30% de S1O2, plus de 15% poids de CaO et plus de 20% d’aluminium, S1O2, CaO et AI2O3 représentant ensemble plus de 70% et de préférence plus de 75% dudit silicate de calcium.
4. Method according to one of the preceding claims, in which a source of calcium is a natural mineral calcium and aluminum silicate comprising, in weight percentage, more than 30% of S1O2, more than 15% by weight of CaO and more of 20% aluminium, S1O2, CaO and Al2O3 together representing more than 70% and preferably more than 75% of said calcium silicate.
5. Procédé selon la revendication 1 dans lequel ladite source de calcium est une matière minérale naturelle répondant à la composition suivante, en pourcentages poids : 5. Method according to claim 1, in which said source of calcium is a natural mineral material having the following composition, in percentages by weight:
- SiC>2 : entre 40 et 60%, de préférence entre 45 et 55%, - SiC>2: between 40 and 60%, preferably between 45 and 55%,
- CaO : entre 10 et 30%, de préférence entre 12 et 20%, - CaO: between 10 and 30%, preferably between 12 and 20%,
- AI2O3 : entre 25 et 35%, - AI2O3: between 25 and 35%,
- S1O2, CaO et AI2O3 représentant ensemble plus de 85%, de préférence encore plus de 90%, voire plus de 95%, - S1O2, CaO and Al2O3 together representing more than 85%, preferably even more than 90%, or even more than 95%,
- Na20 : entre 0 et 4%, - Na20: between 0 and 4%,
- Fe203 : entre 0 et 4%, par exemple entre 0,1 et 1 % - Fe203: between 0 and 4%, for example between 0.1 and 1%
- moins de 5% d’autres oxydes, de préférence moins de 3% d’autres oxydes. - less than 5% of other oxides, preferably less than 3% of other oxides.
6. Procédé dans lequel on utilise comme matières premières dudit bain de fusion une première source de calcium telle que décrite à la revendication 2 ou 3 et une deuxième source de calcium telle que décrite à la revendication 4 ou 5. 6. Process in which a first source of calcium as described in claim 2 or 3 and a second source of calcium as described in claim 4 or 5 are used as raw materials of said molten bath.
7. Procédé selon la revendication précédente, dans lequel ladite source de bore comprend un oxyde de bore et de calcium comprenant, en pourcentage poids, plus de 30% de B2O3 et plus de 20% poids de CaO.7. Process according to the preceding claim, in which the said source of boron comprises an oxide of boron and calcium comprising, in percentage by weight, more than 30% of B2O3 and more than 20% by weight of CaO.
8. Procédé selon l’une des revendications précédentes, dans lequel ledit bain comprend un silicate d’aluminium et de calcium, de préférence tel que décrit selon l’une des revendications 4 à 5 précédentes, et une source de bore constituée par un oxyde de bore et de calcium de préférence selon la revendication 7, en particulier la colémanite. 8. Method according to one of the preceding claims, in which the said bath comprises an aluminum and calcium silicate, preferably as described according to one of the preceding claims 4 to 5, and a source of boron constituted by an oxide boron and calcium preferably according to claim 7, in particular colemanite.
9. Procédé selon la revendication précédente dans lequel ledit bain comprend en outre un silicate de calcium, de préférence tel que décrit selon l’une des revendications 2 ou 3 qui précèdent. 9. Process according to the preceding claim, in which the said bath further comprises a calcium silicate, preferably as described according to one of the preceding claims 2 or 3.
10. Procédé selon l’une des revendications précédentes dans lequel on utilise en outre du kaolin ou de la pyrophyllite comme source d’aluminium. 10. Method according to one of the preceding claims, in which kaolin or pyrophyllite is also used as a source of aluminium.
11. Procédé selon l’une des revendications précédentes, dans laquelle le mélange de matières premières contient moins de 12% poids de CO2, de préférence moins de 10% de CO2, de préférence encore moins de 5% de CO2.
11. Method according to one of the preceding claims, in which the mixture of raw materials contains less than 12% by weight of CO2, preferably less than 10% of CO2, even more preferably less than 5% of CO2.
12. Procédé selon l’une des revendications précédentes, dans lequel on introduit en outre dans le bain de fusion du calcin de verre E ou des fibres minérales recyclés, en particulier de la laine de verre recyclée ou de la laine de roche recyclée. 12. Method according to one of the preceding claims, in which E-glass cullet or recycled mineral fibres, in particular recycled glass wool or recycled rock wool, are also introduced into the molten bath.
13. Procédé selon la revendication précédente, dans lequel le calcin de verre E recyclé ou de fibres minérales recyclées représente entre 10 et 50% du poids total du bain de fusion. 13. Process according to the preceding claim, in which the cullet of recycled E-glass or of recycled mineral fibers represents between 10 and 50% of the total weight of the melt.
14. Procédé selon l’une des revendications 12 ou 13 dans lequel les fibres minérales recyclées présentent la composition suivante : 14. Process according to one of Claims 12 or 13, in which the recycled mineral fibers have the following composition:
SiC>2 : entre 30 et 50%, de préférence entre 35 et 45% SiC>2: between 30 and 50%, preferably between 35 and 45%
Na20: entre 0 et 10%, de préférence entre 0,4 et 7% Na20: between 0 and 10%, preferably between 0.4 and 7%
CaO: entre 10 et 35%, de préférence entre 12 et 25% CaO: between 10 and 35%, preferably between 12 and 25%
MgO : entre 1 et 15%, de préférence entre 5 et 13% MgO: between 1 and 15%, preferably between 5 and 13%
CaO+MgO : entre 11 et 40% en cumulé, CaO+MgO: between 11 and 40% cumulatively,
AI2O3 : entre 10 et 27%, AI2O3: between 10 and 27%,
K2O : entre 0 et 2%, de préférence entre 0 et 1 % K2O: between 0 and 2%, preferably between 0 and 1%
Oxyde de fer : entre 0,1 et 3%, autre (s) oxyde (s) : entre 0 et 5 % en cumulé, de préférence moins de 3%, le reste étant constitué d’impuretés inévitables. Iron oxide: between 0.1 and 3%, other oxide(s): between 0 and 5% cumulatively, preferably less than 3%, the remainder being made up of unavoidable impurities.
15. Mélange de matières premières tel que décrit dans l’une des revendications précédentes 15. Mixture of raw materials as described in one of the preceding claims
16. Mélange de matières premières comprenant : 16. Mixture of raw materials comprising:
- une source de silicium notamment choisie parmi la silice, le calcin de verre E ou des fibres minérales recyclées ou leur mélange, - a source of silicon chosen in particular from silica, E-glass cullet or recycled mineral fibers or a mixture thereof,
- une source de bore de préférence choisie parmi le borax ou un oxyde de bore et de calcium, en particulier la colémanite, ou un oxyde de bore, de sodium et de calcium, en particulier l’ulexite et/ou la tincalconite et/ou la kernite, - a source of boron preferably chosen from borax or a boron and calcium oxide, in particular colemanite, or a boron, sodium and calcium oxide, in particular ulexite and/or tincalconite and/or kernitus,
- au moins une source de calcium choisie parmi un oxyde mixte de calcium avec au moins un élément choisi dans le groupe constitué par Si, Al, en particulier un silicate de calcium et/ou un silicate d’aluminium et de calcium, de préférence un silicate d’aluminium et de calcium,
- optionnellement une source d’aluminium tel que le kaolin, de l’alumine éventuellement hydratée ou la pyrophyllite, - at least one source of calcium chosen from a mixed oxide of calcium with at least one element chosen from the group consisting of Si, Al, in particular a calcium silicate and/or an aluminum and calcium silicate, preferably a aluminum and calcium silicate, - optionally a source of aluminum such as kaolin, optionally hydrated alumina or pyrophyllite,
- optionnellement du calcaire CaC03 ou de l’hydroxyde de calcium Ca(OH)2 ou de la chaux vive CaO, la ou lesdites sources de calcium étant des matières minérales naturelles, c’est à dire issue(s) d’un milieu géologique naturel et non transformées.
- optionally limestone CaC03 or calcium hydroxide Ca(OH)2 or quicklime CaO, said source or sources of calcium being natural mineral materials, ie derived from a geological environment natural and unprocessed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2104437A FR3122418B3 (en) | 2021-04-28 | 2021-04-28 | PROCESS FOR MANUFACTURING E-GLASS FIBERS FROM UNTRANSFORMED MINERAL MATERIALS |
| PCT/FR2022/050819 WO2022229569A1 (en) | 2021-04-28 | 2022-04-28 | Method for manufacturing e-glass fibres from unprocessed mineral materials |
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| EP4330201A1 true EP4330201A1 (en) | 2024-03-06 |
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| CN (1) | CN117222603A (en) |
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| US8746012B2 (en) * | 2007-11-13 | 2014-06-10 | Johns Manville | Composition and method of making a glass product with reduced greenhouse gas emission |
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