PROCESS FOR MANUFACTURING GLASS FIBERS FROM MINERAL MATERIALS INCLUDING ANHYDROUS SODIUM HYDROXIDE

Abstract

The invention relates to a raw material mixture for the preparation of molten glass for the production of glass fibers, having a target composition, comprising the melting of a raw material mixture, in which sodium hydroxide in anhydrous form and preferably in the form of a set of particles with a median diameter d50 of less than 5 millimeters is used as a sodium source.

Description

Title of the invention: PROCESS FOR MANUFACTURING GLASS FIBERS FROM MINERAL MATERIALS INCLUDING ANHYDROUS SODIUM HYDROXIDE

[0001] The invention relates to the field of melting a mixture of raw materials, in particular for the manufacture of glass wool as used in particular in the field of thermal and / or acoustic insulation of buildings or others. According to another aspect, the invention also relates to the manufacture of C glass used in particular in the field of textile fibers and composite materials.

[0002] The manufacture, in particular by the applicant company, of glass wool by melting and fiberizing natural and abundant raw materials (sand or volcanic rock) is a process known and mastered for a long time. The insulating products thus obtained are in the form of a glass wool "mattress" composed of a structure varying from flexible to rigid and trapping air in a stable and immobile manner in the tangle of fibers.

[0003] Glass wool has excellent thermal and acoustic properties which have given it a prominent place in the insulation of residential and non-residential buildings (tertiary, commercial, industrial) for over 80 years. The forms in which glass wool is marketed are varied: rolls, flexible or semi-rigid panels to be unrolled, rigid panels, shells, sheets or flakes.

[0004] Thanks to its tangled structure generating a multitude of small cavities, glass wool is a porous material that traps air. The still air trapped in these pores gives glass wool a strong insulating power with a minimum of material.

[0005] The basis for the manufacture of glass wool or C glass is quarry sand (naturally abundant) to which fluxes such as sodium carbonate and at least one alkaline earth metal are added (to give the glass resistance to hydrolysis) such as limestone (calcium carbonate) and dolomite (CaMg(CO3)2). In some embodiments, boron may also be introduced to give it better chemical and hydrolytic resistance (particularly for C glass) or to improve its thermal properties, particularly for the glass plate. The fiberization is carried out under conditions such that it is complete (no residues such as unmelted material). The fiberization is carried out by centrifugation through perforated plates. The molten material passes into a die and then into continuous fiberization plates from which it emerges in the form of glass threads which are sprayed with polymer (the binder). to form a mattress. After adding binders and other elements specific to each use, the wool mattress is polymerized and calendered.

[0006] In addition to the criteria of quality and industrial and economic feasibility, which have been added in recent years to that of the biodegradable nature of glass wool, namely its capacity to dissolve rapidly in a physiological environment, with a view to preventing any potential pathogenic risk linked to the possible accumulation of the finest fibres in the body by inhalation, a glass wool composition adapted accordingly has been proposed in application EP 399320, to which reference will be made for more details on this technique.

[0007] At the same time, a process is also known for the manufacture of glass fibers, in particular C glass fibers.

[0008] C glass is a glass specially designed for its better chemical resistance to solvents and water. The raw materials are melted and the resulting glass passes through orifices called bushings. The bushings are generally made of Pt. The glass strands, after leaving the bushing, are cooled in air or steam to form a mattress.

[0009] It can be used in the form of a fiber about 5 microns thick and 10 to 4000 microns long, or even up to a few centimeters long.

[0010] The good chemical resistance of borosilicate C glass makes it ideal for use in various applications such as in vinylester paints, acrylic epoxies and acrylic coatings as a barrier against corrosive attack from chemicals and moisture.

[0011] Usually, C glass is also obtained by melting a bath of raw material comprising silica, limestone, feldspar, borax, sodium carbonate and possibly dolomite, the basic components being judiciously chosen to provide a glass composition producing fibers combining flexibility and robustness to mechanical traction as well as to acidic or basic chemical agents.

[0012] The molten mixture (fibreglass for insulation or C glass) is thus usually prepared by melting in a furnace raw materials comprising silica, a source of sodium, most often sodium carbonate Na2CO3, at least one source of alkaline earth (magnesium and / or calcium) in the form of limestone (calcium carbonate) and / or dolomite (CaMg(CO3)2).

[0013] During the melting of the initial mixture for the manufacture of glass wool or C glass, the carbonates release carbon dioxide, the bubbles of which contribute to the mixing of the mass during melting. Furthermore, certain carbonates such as dolomite, even before releasing their CO2, divide into finer particles according to the phenomenon known as decrepitation, which can be quite violent and generate dust which clogs and even corrodes the various conduits equipping the furnaces (chimneys, regenerators, etc.). In a conventional glass wool or C-glass manufacturing process, CO2 emissions due to the melting of raw materials are generally in the order of 10 to 25% of the total mass of raw materials used.

[0014] Furthermore, carbon dioxide is a greenhouse gas and it is desirable to develop mineral wool manufacturing processes that generate as little CO2 as possible for environmental reasons, while leading to a good quality product at an acceptable cost.

[0015] In addition to the release of CO2 directly during the melting process of the raw material bath, it is therefore important to consider the glass manufacturing process as a whole, taking into account other factors such as the cost of the raw materials, their transport, the energy cost of making said raw materials available or even the overall energy expenditure enabling the melting of the mixture.

[0016] As previously indicated, glass is usually prepared by melting in a furnace raw materials comprising a significant portion of carbonates.

[0017] During melting, carbonates release carbon dioxide, the bubbles of which contribute to the stirring of the mass being melted. 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, particularly from the point of view of the energy expenditure required for glass manufacturing.

[0018] In this regard, a phenomenon specific to the melting of glass from an initial mixture of raw materials must be taken into account: foaming.

[0019] Melting the raw materials of the initial mixture requires a significant amount of energy, which is mainly provided by the thermal radiation of the hot combustion products and the heated refractories of the furnace above the melt. The resistance to radiative heating due to the presence of foams is significant and can lead to a 60% decrease in radiative fluxes to the charge and the molten glass. This results in a significant reduction in the energy efficiency of the furnace and an increase in the fuel consumption necessary to reach a sufficient temperature of the molten glass (cf. Glass foams: formation, transport properties, and heat, mass, and radiation transfer; A.G. Fedorov, L. Pilon / Journal of Non-Crystalline Solids 311 (2002) 154-173). It therefore appears that a decrease in the overall energy of the melt requires control of the foaming phenomenon.

[0020] Sodium hydroxide has been proposed as an alternative to sodium carbonate and has the effect of reducing the CO2 generated during glass manufacturing as for example in publications US3753743A or BE761040A. Sodium hydroxide is used in the form of soda lye, with a soda concentration of between 30 and 75% by weight.

[0021] Nevertheless, as described in the remainder of this description, it has appeared that using a sodium hydroxide solution at such a concentration has the consequence of greatly deteriorating the flow of the vitrifiable mixture because it becomes very pasty due to the large quantity of water added and of greatly increasing the energy expenditure necessary for the manufacture of the glass. Also, the chemical homogeneity of the glass has appeared insufficient with such a solution.

[0022] Patent application WO2022 / 229571 also describes the use of sodium hydroxide for the formation of a glass.

[0023] The object of the present invention is to propose a mixture intended for the production of glass comprising boron, in particular for the manufacture of glass fibers, making it possible to solve the preceding problems and in particular to obtain a homogeneous distribution of sodium oxide and silicon oxide in the final glass, while maintaining good flow of the vitrifiable mixture and reducing the energy consumption necessary for said manufacture, in particular by limiting the foaming phenomenon described above.

[0024] Another object of the present invention is to propose a melting method making it possible to preserve the elements of the melting furnace, in particular by limiting the emission of dust into the latter during melting.

[0025] To this end, the experiments carried out by the applicant company have shown the advantages of using sodium hydroxide in anhydrous form as a source of sodium in the initial raw material mixture, in particular if its particle size and preferably its morphology are specifically adapted to such use. Anhydrous form means any source of sodium hydroxide exhibiting a mass loss of less than 5% after heat treatment at 150°C for 1 hour.

[0026] More specifically, the invention relates in particular to a mixture of raw materials for the preparation of a molten glass suitable for the formation of fibers, the target composition of which corresponds to the formulation below, in weight percentage: - SiO2: between 50 and 75%, preferably between 60 and 70% - Na2O: between 10 and 25%, preferably between 10 and 20% - CaO: between 5 and 15%, preferably between 5 and 10% - MgO: between 1 and 10%, preferably between 2 and 5% - CaO and MgO together preferably representing between 5 and 20% - B2O3: between 1 and 10%, preferably between 2 and 8% - A12O3: between 0 and 8%, preferably between 1 and 6% - K2O: between 0 and 5%, preferably between 0.5 and 2% - Na2O and K20 together preferably representing between 12 and 20% - Iron oxide: between 0 and 3%, preferably less than 2%, preferably even less than 1%, - other oxide(s): between 0 and 5% by weight in total, preferably less than 3% in total,

[0027] the remainder being made up of unavoidable impurities.

[0028] Said mixture comprises: - at least one source of silicon chosen in particular from silica, glass cullet, recycled mineral fibres, in particular recycled glass wool, in particular a mixture of silica and glass cullet or a mixture of silica and recycled mineral fibres, or a mixture of silica, glass cullet and recycled mineral fibres, - at least one source of sodium in the form of sodium hydroxide, - at least one source of calcium, preferably chosen from limestone, quicklime or slaked lime or a mixed oxide of calcium with at least one element chosen from the group consisting of Si, Mg, in particular a calcium silicate, said source of calcium being able to be at least partly cullet, - at least one boron carrier, preferably chosen from a boron oxide such as pentaborax or a mixed oxide of boron with at least one element chosen from the group consisting of Si, Mg, Ca, in particular an oxide chosen from the group consisting of colemanite, ulexite, tincalconite or kemite, - optionally at least one source of magnesium preferably chosen from dolomite, possibly calcined, magnesite (MgCO3), brucite (Mg(OH)2) or a mixed oxide of magnesium with at least one element chosen from the group consisting of Si, Ca, in particular a magnesium silicate, - optionally at least one compound chosen from the group consisting of feldspar, in particular of formula (K,Na)AlSi3O8, nepheline or phonolite, - optionally recycled glass cullet, - optionally a milkman

[0029] wherein the sodium hydroxide is in anhydrous form.

[0030] Preferably the mixture is made up, for more than 90% by weight or even more 95% by weight, preferably more than 99% by weight, of the constituents mentioned above.

[0031] In said mixture according to the invention, the sodium hydroxide is in anhydrous form, in particular in the form of anhydrous particles, and preferably in the form of a set of particles with a median diameter d50 of less than 5 millimeters, preferably less than 2 millimeters, more preferably less than 1.5 millimeters.

[0032] In the present description, the term "particle" describes an individualized entity of anhydrous sodium hydroxide.

[0033] By the expression "for the preparation of a molten glass of target composition", it is meant that the various raw materials previously cited are present in said mixture in proportions suitable for the final production, after melting according to the techniques of the art, of the glass of the target composition described above.

[0034] This mixture of raw materials is therefore intended to be heated to a temperature and under conditions allowing its melting to obtain a glass corresponding to said target composition and its drawing in the form of the fibers previously described.

[0035] According to particular and advantageous embodiments of the present invention which can of course be combined with each other if necessary: - Said set of particles have an average circularity greater than 0.70, preferably greater than 0.75, or even greater than 0.80. - Anhydrous sodium hydroxide is in the form of a set of particles whose average Feret diameter is less than 5 millimeters, preferably less than 3 millimeters, or even less than 2 millimeters. - Anhydrous sodium hydroxide is in the form of a set of particles whose average equivalent diameter is less than 5 millimeters, preferably less than 3 millimeters, or even less than 2 millimeters. - Anhydrous sodium hydroxide is in the form of a set of particles whose average aspect ratio is less than 1.30, preferably less than 1.20. - Anhydrous sodium hydroxide comprises a total water proportion of less than 30% by weight, preferably less than 25% by weight. - Sodium hydroxide is the only source of sodium (apart from possible additions of cullet or feldspar, nepheline or phonolite). - Alternatively, the sodium is provided in the form of a mixture of sodium hydroxide and sodium carbonate Na2CO3, the anhydrous sodium hydroxide according to the invention preferably representing more than 20% by weight of said mixture, or even more than 50% by weight of said mixture. - A source of calcium is a mineral calcium silicate, preferably natural. - A source of calcium is calcium oxide. - A source of calcium is calcium hydroxide. - A source of magnesium is a mineral magnesium silicate, preferably natural. - A source of calcium is a mineral calcium silicate, preferably natural, comprising, in weight percentage, more than 30% of SiO2 and more than 10% of CaO, preferably more than 15% of CaO, CaO and SiO2 together representing more than 60%, or even more than 70% or even more than 80% of the total weight of said source. - A source of magnesium is a mineral magnesium silicate, preferably natural, comprising, in weight percentage, more than 30% of SiO2 and more than 10% of MgO, preferably more than 15% of MgO, MgO and SiO2 together representing more than 60%, or even more than 70% or even more than 75% of the total weight of said source. - A source of magnesium is brucite Mg(OH)2. - The raw materials of said molten bath comprise a source of calcium as previously described and a source of magnesium as previously described. - A source of potassium is potassium hydroxide.

[0036] According to the invention, said raw materials, in particular the mineral oxides such as the silicates mentioned above, are natural. In particular, according to the invention, natural silicates can be used, that is to say in their initial geological composition after their extraction from their deposit, in particular without chemical alteration aimed at modifying the initial composition, that is to say mineral materials not chemically transformed. In particular, according to the method of the present invention, the initial basis is the exact composition of these untransformed geological mineral materials, as precisely determined by any suitable technique (for example chemical analysis, X-ray diffraction, etc.) to determine the composition of the initial bath. However, they can of course undergo steps prior to their use as raw material for fusion but without chemical transformation of the crystalline grains constituting them.Such steps may be crushing, screening, washing or even flotation, magnetic separation or any other physical separation of impurities present between said grains of the natural mineral matter.

[0037] Silica is generally introduced into the raw material mixture in the form of sand.

[0038] If necessary, as indicated above, the mixture of raw materials can also advantageously comprise an Al carrier, a precursor of alumina in the glass, such as a feldspar or alternatively a blast furnace slag for example.

[0039] 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 alkali carbonate and alkaline earth carbonate is less than 30%, and preferably less than 10%, and preferably less than 5%, and preferably less than 1% by weight, or is even zero in the mixture of raw materials. According to a possible advantageous embodiment, the mixture of raw materials may be substantially free of any carbonate. It is advantageously capable of releasing only a minimal portion of carbon oxide during its heating and melting into glass due, for example, to the addition of coke to the initial mixture.

[0040] To produce the glass, the Si carrier is introduced into the mixture of raw materials in the form of sand, the alkali carriers are advantageously introduced into the mixture of raw materials in the form of hydroxides, in particular in the form of anhydrous NaOH and preferably of a particle size adapted according to the invention. The possible aluminum carrier can be introduced into the mixture of raw materials in the form of feldspar powder.

[0041] Each raw material is introduced into the raw material mixture in such an amount that the molar percentage of its cation (such as Si, Na, Mg, Ca, B, K Al, etc.) relative to the sum of the moles of all cations is the same as in the final glass. As previously indicated, the raw materials in the mixture are chosen to lead to a glass whose target composition falls within the framework (the percentage ranges for the different oxides) described previously.

[0042] The mixture of raw materials is heated until a molten glass is obtained, generally in a furnace. The heating is carried out at a higher or lower temperature and for a longer or shorter time depending on the quality of the glass required, in particular depending on the degree of tolerance for unmelted particles (called "unmelted") and bubbles. Generally, the maximum heating temperature of the molten glass is between 1200 and 1700°C. For the transformation of the mixture of raw materials into glass, glass melting techniques well known to those skilled in the art can be used. This transformation can be carried out in any type of furnace such as an electric electrode furnace, an overhead burner furnace such as a transverse burner furnace or a loop furnace, or a submerged burner furnace.

[0043] For heating and melting into glass, the mixture of raw materials may be introduced into a furnace in a powdered state, which implies that each raw material it contains is in a powdered state. For heating and melting into glass, the mixture of raw materials may be introduced into a furnace in a compositional state comprising cullet and said mixture of raw materials, the latter being, where appropriate, powdered.

[0044] The invention also relates to a method for manufacturing a glass having this same target composition, comprising the melting of a mixture of raw materials, said mixture constituting a melt bath, said method comprising the following steps:

[0045] a) the necessary quantities of said raw materials are selected to obtain, after melting, a glass of said target composition, said raw materials being chosen from at least: - at least one source of silicon chosen in particular from silica, glass cullet, recycled mineral fibres, in particular recycled glass wool, in particular a mixture of silica and glass cullet or a mixture of silica and recycled mineral fibres, or a mixture of silica, glass cullet and recycled mineral fibres, - at least one source of sodium in the form of sodium hydroxide - at least one source of calcium, preferably chosen from limestone, quicklime or slaked lime or a mixed oxide of calcium with at least one element chosen from the group consisting of Si, Mg, in particular a calcium silicate, said source being able to be at least partly cullet, - at least one boron carrier, preferably chosen from a boron oxide such as pentaborax or a mixed oxide of boron with at least one element chosen from the group consisting of Si, Mg, Ca, in particular an oxide chosen from the group consisting of colemanite, ulexite, tincalconite or kemite, - optionally at least one source of magnesium preferably chosen from dolomite, possibly calcined, magnesite (MgCO3), brucite (Mg(OH)2) or a mixed oxide of magnesium with at least one element chosen from the group consisting of Si, Ca, in particular a magnesium silicate, - optionally at least one compound chosen from the group consisting of feldspar, in particular of formula (K,Na)AlSi3O8, nepheline or phonolite, - optionally recycled glass cullet, - optionally a milkman,

[0046] b) said mixing of said raw materials is carried out according to said quantities,

[0047] c) said mixture is melted and cooled under conditions allowing said glass to be obtained,

[0048] wherein said sodium hydroxide in said mixture is in anhydrous form, particularly in the form of anhydrous particles. Preferably, the sodium hydroxide sodium is in the form of a set of particles with a median diameter d50 of less than 5 millimeters, preferably less than 2 millimeters, more preferably less than 1.5 millimeters, more preferably less than 1 millimeter. Examples

[0049] In the following examples, different mixtures of raw materials were prepared in order to compare a mixture as currently used for the manufacture of glass for an identical final glass composition, which has substantially the following composition:

[0050] [Tables 1] Elements Percentage wt% SiO2 65.0 CaO 6.7 B2O3 5.6 Na2O 15.7 MgO 2.8 A12O3 2.5 Fe2O3 <1 k2o 0.7 Other oxy Impurities

[0051] Table 2 below gives the proportions of the different raw materials for the 5 mixtures prepared:

[0052] [Tables2] Mix A Mix B Mix C Mix D kg / ton glass kg / ton glass kg / ton glass kg / ton glass Sand 543 543 543 543 Feldspar 151 151 151 151 Sodium carbonate 208 Sodium hydroxide 1 314 Sodium hydroxide 2 157 Sodium hydroxide 3 157 Calcined dolomite 74 74 74 74 Limestone 41 41 41 41 Borax pentahydrate 127 127 127 127

[0053] The mixtures are differentiated by the particle size and the size of the sodium hydroxide source used.

[0054] The particle size and the different geometric characteristics of the different forms of sodium hydroxides used were determined by image analysis using ImageJ® software. The median diameter, the Feret diameter, the circularity and the aspect ratio are thus determined for each of the sodium hydroxides and their values ​​are given in Table 3 below.

[0055] More precisely:

[0056] The circularity of a particle is given by the formula S = 4ir (A / P2), with A area and P the perimeter of said particle.

[0057] The Feret diameter is classically defined as the distance between two parallel tangents to the periphery of the projected surface of the particle in a direction, such that the entire projection of the particle is between these two parallels.

[0058] The median diameter d50 of each sodium hydroxide sample is also measured by image analysis using ImageJ ® software.

[0059] The equivalent diameter of a particle is defined as the diameter of a circle whose perimeter is equivalent to the perimeter of said particle, as measured on said images.

[0060] The aspect ratio of a particle is the ratio between its greatest length and its shortest length.

[0061] An average circularity, Feret diameter, equivalent diameter and aspect ratio are then defined for all the particles in each sodium hydroxide sample, as shown in Table 3 below.

[0062] The proportions of free water and bound water of these different qualities of sodium hydroxide are also reported there.

[0063] Conventionally, the median diameter is the diameter for which 50% of the particles in number have a diameter less than this diameter and 50% a diameter greater than this diameter.

[0064] [Tables3] Mixture B Mixture C Mixture D Sodium Hydroxide m 1 Sodium Hydroxide m 2 Sodium Hydroxide 3 Media diameter nd50 - 929pm 5325pm Ferret diameter - 995pm 5775pm Equivalent diameter - 995pm 6210pm Circularity - 0.85 0.75 Aspect ratio - 1.14 1.11 Total water 61.5% 23% 23% Free water 50% Less than 2% Less than 2% Bound water 11.5% remainder remainder

[0065] Total water corresponds to the set of free water plus bound water.

[0066] The percentage of bound water is therefore obtained by subtracting the percentage of free water from the percentage of total water (“remainder” in table 3 above).

[0067] Bound water means water chemically bound to the structure via strong bonds, i.e. typically the hydroxyl group -OH in a general formulation NaOH. The temperature for removal of bound water (dehydroxylation) is well above 100°C. In the case of dehydroxylation of anhydrous sodium hydroxide, the water released is essentially bound water according to the formula 2NaOH to Na2O + H2O).

[0068] By anhydrous form is meant in particular any source of sodium hydroxide exhibiting a mass loss of less than 5%, preferably less than 2%, after heat treatment at 150°C for 1 hour.

[0069] By free water, on the contrary, is meant all the water molecules bound by weak interactions. Free water can, for example, correspond to the water of solution in which sodium hydroxide is present as described in application US3753743A but also to the water present between the sodium hydroxide particles, in particular due to the hygroscopic nature of this compound. Unlike bound water, this water is weakly bound to sodium hydroxide by weak bonds.

[0070] Thus, an “anhydrous” sodium hydroxide comprises less than 5% free water and preferably less than 2% free water, in the sense previously described.

[0071] For the purposes of the present invention, a sodium hydroxide is therefore said to be anhydrous when it comprises less than 5% free water.

[0072] Mixture B is in accordance with the teaching of publication US3753743A. Mixture C is in accordance with the subject of the present invention. Examples A and D are comparative examples. Example A is a comparative example in which sodium carbonate is conventionally used as the sodium source.

[0073] The performances and qualities of the mixtures of raw materials according to the preceding examples A to D, including the quality of the glass after their melting, are measured according to the following different criteria:

[0074] 1°) Flow measurement by the slope angle and rotating drum tests

[0075] The angle of repose and the rotating drum are methods of evaluating the powder flowability, carried out by predicting the flow of vitrifiable mixtures at the mixer outlet until loading.

[0076] These techniques make it possible to estimate, with respect to the reference mixture (mixture A), the way in which the other vitrifiable mixtures flow. If the flow is weak or poor, the risks of clogging on the conveyor belts or in the loading hoppers are greater.

[0077] As for the angle of slope, the vitrifiable mixture is introduced into a trapdoor funnel. Then the trapdoor is removed to allow the vitrifiable mixture to flow onto a sheet of graph paper, which results in a cone. The height of the cone is measured and its circumference is plotted on the graph paper to then deduce its average diameter. Finally, with the height and diameter of the cone, the angle of slope of the vitrifiable mixture is calculated according to the formulas: Angle of slope (degrees) = 180 x Arc Tangent (height of slope / (1 / 2 x diameter of cone)) / jt. The interpretation of the measurement results is made on the basis of the classification present in the Engineering Technique - Forming of solids. Ref J3380 VL

[0078] The results obtained are grouped in Table 4 below.

[0079] The reference mixture (Mixture A) has a very good flow, just like mixture C, with angles of slope between 25 and 30° (see the Technical classification of the engineer - Forming of solids. Ref. J3380 VI). Mixture D has a good flow with an angle of slope of 32°. On the other hand, with its angle of slope greater than 50°, mixture B has a poor flow and suggests the use of suitable devices to assist discharge in the event of the mixture passing into a hopper, for example. In addition, the risks of clogging of the mixer or of blockages on the conveyor belts are high in the case of mixture B.

[0080] The rotating drum used is the Revolution powder analyzer. It allows the ability of a powder to flow to be assessed by rotating a drum containing the powder mixture in question. The drum has two glass sides to allow observation of the flow of the powder mixture. A digital camera with backlighting takes images during rotation, at a speed chosen here of 1 revolution per minute (rpm). The Revolution powder analyzer then makes it possible to evaluate the power of the avalanches, which is calculated here as the maximum potential energy before the occurrence of an avalanche, called break energy. The higher this is, the less freely the powder mixture flows. 150 avalanches are considered for each of the mixtures in order to average this break energy. Mixtures B, C and D were characterized and the results obtained are presented in Table 4 below. Mixture C according to the invention has the lowest potential energy and can therefore be considered as the one that flows most freely.

[0081] [Tables4] Mixture A Mixture B Mixture C Mixture D Angle of repose 25° >50° 23° 28° Fracture energy (relative to Mixture A) Reference No flow -6% -3%

[0082] 2°) Measurement of emissivity

[0083] A mixture of low-emissivity raw materials produces a thermal mirror on the surface of the composition lump, which reduces the melting kinetics and increases the energy consumption of the furnace to achieve the same degree of melting.

[0084] The emissivity of the different mixtures indicated in Table 5 below was measured from the reflectance spectra using the law of conservation of energy for opaque materials: absorbance a(X, T) + reflectance p(X, T) = 1. By applying Kirchhoff's law, the spectral emittance can be expressed in terms of total reflectance,

[0085] e(X, T) = a(X, T)

[0086] with:

[0087] where Bt is the spectral irradiance of the black body at temperature T of 2000°C, corresponding to the temperature of the air-gas flame of the burner.

[0088] Room temperature hemispherical reflectance measurements are performed with a 150 mm integrating sphere mounted on a Lambda spectrophotometer between 300 and 2500 nm, using a Spectralon plate as a reflectance reference.

[0089] For easy handling, the vitrifiable mixture samples are pressed by applying a force of 0.4 tonnes / cm2 and wetted with 2% water prior to measurement.

[0090] [Tables5] Mixture A Mixture B Mixture C Mixture D Emissivity 0.30 nd >0.4 >0.4

[0091] In order to improve the heat transfer between the flame and the glass, the person skilled in the art seeks to maximize the emissivity of the batch as much as possible. Too low an emissivity is a sign of high thermal reflectivity which could result in a screening effect. This will produce an increase in the temperature of the roof and a low temperature of the glass bath. The data in Table 5 show that the use of NaOH improves the thermal absorption of the batch compared to the use of sodium carbonate (mixture A).

[0092] 3°) Icing

[0093] Glazing the composition lumps is an essential element in order to limit the emission of dust from the powdery batch of raw materials. Indeed, during the charging and melting of the mixture of raw materials within the glass furnace, the vitrifiable mixture sees high temperatures, typically above 1200°C, which lead to a partial melting of the raw materials and the formation of a first liquid, in particular on the surface of the composition lumps exposed to the radiation of the burners. This phenomenon, called glazing, is essential to limit the exposure of the mixture of powdery materials that have not yet reacted (and are located under the glazed crust) to the shear currents imposed by the burners within the furnace.

[0094] Thus, lumps of composition having a higher rate of glazing of their surface (and conversely a proportion of craters from which the powdery batch could be easily lifted by the gas flows within the furnace), will be more capable of limiting the emission of dust by shearing.

[0095] The mixtures of raw materials are prepared according to the proportions indicated in Table 2, then are homogenized for 60 seconds in a turbula. The mixtures are then placed in Platinum crucibles and are placed in an electric furnace regulated at 1300°C for a period of 8 minutes in order to simulate the placing of such a vitrifiable mixture in a glass furnace. At the end of these 8 minutes, the crucibles are removed from the furnace and placed in ambient air until they cool. No annealing is carried out.

[0096] Two techniques are used to describe the quality of the icing: - An analysis of the surface of the samples using ImageJ software to determine the proportions of craters (powder batch) and crust (glazing). Here the surface proportion of crater is determined as the ratio between the surface of the craters divided by the total surface. - Determination of crust thickness by ultrasonic measurements (c=5000m / s)

[0097] The results are reported in Table 6 below:

[0098] [Tables] Mix A Mix B Mix C Mix D Thickness Glaze Reference >Ref >Ref >B >Ref >B Surface proportion of craters (crater surface / total surface) 25.2% nd 1.4% 5.3%

[0099] It appears that the product obtained from mixture C has both a greater crust thickness and a lower surface proportion of craters, which makes it possible to minimize the rates of flight within the furnace.

[0100] 4°) Energy required for fusion

[0101] A reduction in energy consumption logically leads to a reduction in costs (less energy to be used to melt the mixture of raw materials) and in the carbon footprint of glass production (less gas to be used, for example).

[0102] The energy required for melting the different raw material mixtures was determined using FactSage 8.0 software. The energy is calculated over the temperature range 25 and 1400°C.

[0103] The results of the evaluation are reported in Table 7 below:

[0104] [Tables7] Mix A Mix B Mix C Mix D Evolution of energy consumption vs. mix A Reference +30% -13% -13%

[0105] Table 7 shows that with mixture B (50% free water), the fusion energy of the vitrifiable mixture is drastically increased: +30% compared to the reference (mixture A). On the contrary, with the other mixtures, including mixture C according to the invention, the energy consumption is significantly reduced compared to this same reference, by approximately 13%.

[0106] 5°) Homogeneity of the glass obtained after melting

[0107] Non-homogeneous glass exhibits “waves” (optical defects), i.e. areas where the refractive index varies locally due to a variation in chemical composition.

[0108] Glass samples were melted in a cylindrical platinum crucible from the mixtures indicated in Table 2. Each sample was heated in air at 1480°C for 2 hours. The cooled glass was then cored and cut to obtain a blade comprising the cross-section of the cylinder. This blade was polished, carbon-metallized and analyzed using an electron microprobe at 15 kV. The analysis consisted of determining the mass percentages of Na2O, CaO and SiO2 over the height of the blade (or of the melted sample) at 50 measurement points, the measurement interval being 500 microns.

[0109] It is thus possible on this basis to calculate the average of the concentration of Na2 O, CaO and SiO2 and the standard deviations. A criterion of homogeneity in Na2O, CaO and SiO2 in the glass is provided by the standard deviation ratio divided by the average concentration (oNa2 O / [Na2O], oCaO / [CaO] and oSiO2 / [SiO2]).

[0110] The results obtained are reported in Table 8 below. [YES] [Tables8] Mix. A Mix. B Mix. C Mix. D Glass homogeneity (standard deviation / mean) Na2O 1.9% 1.5% 0.8% 0.8% CaO 4.2% 4.6% 2.0% 1.9% SiO2 1.0% 1.0% 0.5% 0.5%

[0112] The homogeneity of sodium oxide and silicon oxide appears particularly improved in the case of mixture C according to the invention.

[0113] 6°) Foaming

[0114] Foam constitutes a major resistance to heat transfer from the combustion zone. This screening induced by foam therefore has a detrimental effect on the energy efficiency of the furnace, the quality of the final glass as well as the lifetime of the furnace.

[0115] Foaming was evaluated in an electric furnace on mixtures A and C. To do this, each mixture was heated to a temperature of 1350°C for 1 hour. At the end of melting, the maximum foaming heights reached during melting were measured. They correspond to the difference between the height of the glass considering the foam and the height of the final glass. The values ​​obtained are reported in Table 9.

[0116] [T ableaux9] Temperature Mix. A Mix. C Foam thickness in electric oven (mm) 1350°C 36.4 33.9

[0117] Foaming appears particularly reduced in the case of mixture C, which implies less thermal screening induced by the foam and therefore better energy efficiency of the furnace.

[0118] All of the results previously set out and the advantages of the present invention, materialized by the superiority of mixture C according to the invention, are summarized below:

[0119] - good flow of the raw material mixture,

[0120] - better icing of the composition lumps during melting, which allows limit dust emissions into the melting furnace and thus preserve its elements

[0121] - an improved emissivity of the vitrifiable mixture, which implies a better transfer thermal effect of flames on the mixture of raw materials during melting

[0122] - Limited foaming during the melting of the raw material mixture, resulting in less thermal screening,

[0123] - A significant decrease in the overall fusion energy of the mixture

[0124] - Better homogeneity of the glass finally obtained.

Claims

1. Claims Mixture of raw materials for the manufacture of glass, in particular glass fibers, having a target composition, said target composition corresponding to the following formulation: - SiO2: between 50 and 75%, preferably between 60 and 70% - Na2O: between 10 and 25%, preferably between 10 and 20% - CaO: between 5 and 15%, preferably between 5 and 10% - MgO: between 1 and 10%, preferably between 2 and 5% - CaO and MgO together preferably representing between 5 and 20% - B2O3: between 1 and 10%, preferably between 2 and 8% - A12O3: between 0 and 8%, preferably between 1 and 6% - K2O: between 0 and 5%, preferably between 0.5 and 2% - Na2O and K2O together preferably representing between 12 and 20% - Iron oxide: between 0 and 3%, preferably less than 2%, even more preferably less than 1%, - other oxide(s): between 0 and 5% by weight in total, preferably less than 3% in total, the remainder being made up of unavoidable impurities, said mixture comprising#: - a source of silicon chosen in particular from silica, glass cullet, recycled mineral fibres, in particular recycled glass wool, in particular a mixture of silica and glass cullet or a mixture of silica and recycled mineral fibres, or a mixture of silica, glass cullet and recycled mineral fibres, - at least one source of sodium in the form of sodium hydroxide, - at least one source of calcium, preferably chosen from limestone, quicklime or slaked lime or a mixed oxide of calcium with at least one element chosen from the group consisting of Si, Mg, in particular a calcium silicate, said source also being able to be at least partly cullet, - at least one boron carrier, preferably chosen from a boron oxide such as pentaborax or a mixed boron oxide with at least one element chosen from the group consisting of Si, Mg, Ca, in particular an oxide chosen from the group consisting of colemanite, ulexite, tincalconite or kemite, - optionally at least one magnesium source preferably chosen from dolomite, optionally calcined, magnesite or a mixed magnesium oxide with at least one element chosen from the group consisting of Si, Ca, in particular a magnesium silicate, - optionally at least one compound chosen from the group consisting of feldspar, in particular of formula (K,Na)AlSi3O8, nepheline or phonolite, - optionally slag, - optionally recycled glass cullet, characterized in that the sodium hydroxide is in anhydrous form.

2. Mixture according to claim 1, in which the anhydrous sodium hydroxide is in the form of a set of particles having a median diameter d50 of less than 5 millimeters, preferably less than 2 millimeters, more preferably less than 1.5 millimeters.

3. A mixture according to claim 1 or 2, wherein the anhydrous sodium hydroxide is in the form of a set of particles having an average circularity greater than 0.70, preferably greater than 0.75, or even greater than 0.

80.

4. Mixture according to one of the preceding claims, in which the anhydrous sodium hydroxide is in the form of a set of particles whose average Feret diameter is less than 5 millimeters, preferably less than 3 millimeters, or even less than 2 millimeters.

5. Mixture according to one of claims 1 to 3, in which the anhydrous sodium hydroxide is in the form of a set of particles whose average equivalent diameter is less than 5 millimeters, preferably less than 3 millimeters, or even less than 2 millimeters.

6. A mixture according to any preceding claim, wherein the anhydrous sodium hydroxide is in the form of a set of particles whose average aspect ratio is less than 1.30, preferably less than 1.

20.

7. Mixture according to one of the preceding claims, in which the anhydrous sodium hydroxide comprises a total water proportion of less than 30% by weight, preferably less than 25% by weight.

8. Mixture according to one of the preceding claims, in which said anhydrous sodium hydroxide is the only source of sodium, apart from any additions of cullet or feldspar, nepheline or phonolite.

9. Mixture according to one of the preceding claims, in which the sodium is provided in the form of a mixture of anhydrous sodium hydroxide and sodium carbonate Na2CO3, the anhydrous sodium hydroxide preferably representing more than 20% by weight of said mixture, or even more than 50% by weight of said mixture.

10. Mixture according to one of the preceding claims, in which a source of calcium is a mineral calcium silicate comprising, in weight percentage, more than 30% of SiO2 and more than 10% of CaO, preferably more than 15% of CaO, CaO and SiO2 together representing more than 60%, or even more than 70% or even more than 80% of the total weight of said source.

11. Mixture according to one of the preceding claims, in which a source of magnesium is a mineral magnesium silicate comprising, in weight percentage, more than 30% of SiO2 and more than 10% of MgO, preferably more than 15% of MgO, MgO and SiO2 together representing more than 60%, or even more than 70% or even more than 75% of the total weight of said source.

12. A mixture according to any preceding claim, wherein a source of potassium is potassium hydroxide.

13. A mixture according to any preceding claim, wherein a source of calcium is calcium hydroxide.

14. A mixture according to any preceding claim, wherein a source of magnesium is magnesium hydroxide.

15. A method of manufacturing a glass having a target composition, comprising melting a mixture of raw materials according to one of the preceding claims, said mixture constituting a melt bath, said target composition meeting the following criteria, in weight percentages: - SiO2: between 50 and 75%, preferably between 60 and 70% - Na2O: between 10 and 25%, preferably between 10 and 20% - CaO: between 5 and 15%, preferably between 5 and 10% - MgO: between 1 and 10%, preferably between 2 and 5% - CaO and MgO together preferably representing between 5 and 20% - B2O3: between 1 and 10%, preferably between 2 and 8% - A12O3: between 0 and 8%, preferably between 1 and 6% - K2O: between 0 and 5%, preferably between 0.5 and 2% - Na2O and K2O together preferably representing between 12 and 20% - Iron oxide: between 0 and 3%, preferably less than 2%, even more preferably less than 1%, - other oxide(s): between 0 and 5% by weight in total, preferably less than 3% in total, said method being characterized in that it comprises the following steps: a) the necessary quantities of said raw materials constituting said mixture are selected to obtain, after melting, a glass of said target composition, said raw materials being chosen from at least: - a source of silicon chosen in particular from silica, glass cullet, recycled mineral fibres, in particular recycled glass wool, in particular a mixture of silica and glass cullet or a mixture of silica and recycled mineral fibres, or a mixture of silica, glass cullet and recycled mineral fibres, - at least one source of sodium in the form of sodium hydroxide, - at least one source of calcium, preferably chosen from limestone, quicklime or slaked lime or a mixed oxide of calcium with at least one element chosen from the group consisting of Si, Mg, in particular a calcium silicate, said source also being able to be at least partly cullet, - at least one boron carrier, preferably chosen from a boron oxide such as pentaborax or a mixed boron oxide with at least one element chosen from the group

16. consisting of Si, Mg, Ca, in particular an oxide chosen from the group consisting of colemanite, ulexite, tincalconite or kemite, - optionally at least one source of magnesium preferably chosen from dolomite, possibly calcined, magnesite or a mixed oxide of magnesium with at least one element chosen from the group consisting of Si, Ca, in particular a magnesium silicate, - optionally at least one compound chosen from the group consisting of feldspar, in particular of formula (K,Na)AlSi3O8, nepheline or phonolite, - optionally slag, - optionally recycled glass cullet, b) said mixing of said raw materials is carried out according to said quantities, c) the said mixture is melted and cooled under conditions allowing the said glass to be obtained, in which the sodium hydroxide in the said mixture is anhydrous. Manufacturing process according to the preceding claim, in which the anhydrous sodium hydroxide is in the form of particles having a median diameter d50 of less than 5 millimeters, preferably less than 2 millimeters, more preferably less than 1.5 millimeters.