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  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    The present invention relates to a method for preparing glass frits by supplying the total energy required in the process by means of concentrated solar radiation. It is further related with a device for carrying out said method comprising elements such as a solar flat mirror, a solar beam shutter and a solar radiation concentrator. The device further includes means for storing, feeding and containing the raw materials. Several advantages are derived from the use of the method and device of the present invention, which can be summarized in a reduction in energy consumption and an increased productivity of the process.
    公开号:ES2732490A2
    申请号:ES201990069
    申请日:2018-03-05
    公开日:2019-11-22
    发明作者:Perez Maximina Romero；Delgado Aurora Lopez；Villalva Jose Ignacio Robla
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

    [0001]
    [0002]
    [0003]
    [0004] The present invention falls within the field of manufacturing glass frits.
    [0005]
    [0006] The first object of the present invention is a method for preparing glass frits by supplying the total energy required in the process by means of concentrated solar radiation.
    [0007]
    [0008] Another object of the present invention is a device for carrying out said method comprising elements such as a flat solar mirror, a solar light beam shutter and a solar radiation concentrator. The device also includes means for storing, feeding and containing raw materials, such as
    [0009] - a hopper for raw materials
    [0010]
    [0011] - a raw material feeder
    [0012]
    [0013] - a crucible with a tilting arm located at the focal point of concentrated solar radiation
    [0014] - a water tank to pour molten raw materials with an articulated support.
    [0015]
    [0016] STATE OF ART
    [0017]
    [0018] Glass frits are vitreous materials prepared by high temperature fusion of a mixture of raw materials. Frits are the main component of almost all ceramic glazes. They are also present in many of the compositions of different materials in which a vitreous phase is needed as a binder. Currently, there are many varieties of frits in the market, with different physicochemical characteristics: composition, phases, melting point, hardness, color, resistance to erosion, brightness, opacity, hue, etc.
    [0019]
    [0020] Today, the production of frits is carried out in continuous melting furnaces and the common temperatures in the furnaces range between 1350 ° and 1550 ° C. Once the raw material loads have melted, the melt rapidly cools in water; In this way, the melt solidifies into small pieces of glass. East Fusion process implies significant energy consumption and low efficiency and productivity of the process.
    [0021] The manufacture of frits is an intensive energy process, which requires high temperatures usually supplied by the combustion of fossil fuels. The highest energy consumption of the process occurs within the melting furnace; In general, the energy required for fusion represents more than 75% of the total energy consumed in the frit manufacturing process. The theoretical energy required to convert the mixture of raw materials into glass is about 2.7 GJ / t [(Trier, W., Glass Furnaces: Design Construction and Operation, Sheffield: Society of Glass Technology, 1987, p. ( Scalet, BM, et al., 2013. European Commission, Best Available Techniques (BAT), reference document for the manufacture of glass).
    [0022]
    [0023] This theoretical value only takes into account the chemical heat of reaction and enthalpy changes associated with the heating of the raw material load from room temperature to melting temperature. However, from a practical point of view it is necessary to overcome the heat losses related to maintaining the melting temperature of the glass. Actual energy consumption for glass melting in modern industry can vary from 3.5 to 40 GJ / t depending on the oven design and scale [see the previous reference of Scalet B.M. Et al. (2013)].
    [0024]
    [0025] The main drawbacks of the current procedure are: high cost of furnaces, high energy consumption, low productivity in Kg / h • KJ and high CO2 production. Therefore, it is of great importance to look for new sustainable processes to reduce energy requirements and also eliminate fossil fuel consumption. Important research has been carried out aimed at the use of concentrated solar energy (ESC) in different industrial processes, such as
    [0026]
    [0027] - lime production from limestone [A. Meier, N. Gremaud, A. Steinfeld. Energy conversion and management 46 (2005) 905],
    [0028]
    [0029] - alumina from boehmite [I. Padilla, A. López-Delgado, S. López-Andrés, M. Álvarez, R. Galindo, A.J. Vázquez-Vaamonde. The Scientific World Journal (2014); http://dx.doi.org/10.1155/2014/825745] and
    [0030]
    [0031] - anhydrite from plaster [A. López-Delgado, S. López-Andrés, I. Padilla, M. Álvarez, R. Galindo, AJ Vázquez. Geomaterials 4 (2014) 82].
    [0032] Concentrated solar energy has also been applied in the following processes:
    [0033] - sintered alumina [R. Román, I. Cañadas, J. Rodríguez, M.T. Hernández, M. González. Solar sintering of alumina ceramics: Microstructural development. Solar Energy 82 (2008) 893-902] and
    [0034]
    [0035] - cordierite-based ceramics [F. Almeida, N. Shohoji, J. Cruz, L. Guerra. Solar sintering of cordierite-based ceramics at low temperatures. Solar Energy 78 (2005) 351 361]
    [0036]
    [0037] as well as in metallurgical processes such as:
    [0038] - cast aluminum from aluminum scrap [Funken, K.-H. et al., 2001. Aluminum remelting using directly solar heated rotary kilns. ASME J. Solar Energy Eng.
    [0039] 123, 117-124],
    [0040]
    [0041] - production of titanium foams [I. García, E. Gracia-Escosa, M. Bayoda, A. Conde, M.A. Arenas, J. Damborenea, A. Romer, G. Rodríguez. Sustainable production of titanium foams for biomedical applications by Concentrated Solar Energy sintering. Materials Letters 185 (2016) 420-423],
    [0042]
    [0043] - recovery of zinc from materials containing zinc [Tzouganatos, N. et al.
    [0044] 2013. Thermal recycling of Waelz oxide using concentrated solar energy J. Met. 65, 1733-1743],
    [0045]
    [0046] - mild steel [A. Vázquez, G. P. Rodríguez, J. de Damborenea.Solar EnergyMaterials24 (1991) 751],
    [0047]
    [0048] - production of titanium nitride [C. Sierra, A. J. Vázquez; Solar Energy Materials and Solar Cells 86 (2005) 86] and
    [0049]
    [0050] - stainless steel [J. from Damborenea, A.J. Vázquez, B. Fernandez, Materials & Design15 (1994) 41]
    [0051]
    [0052] - coatings, welding of steels and titanium alloys [A. Rosemary. I. García, M. A. Arenas, V. López, A. Vázquez. Solar Energy 95 (2013) 131] and
    [0053]
    [0054] - thermal shock tests on intermetallic materials [D.G. Morris, A. López-Delgado, I. Padilla, M.A. Muñoz-Morris. Solar Energy 112 (2015) 246].
    [0055]
    [0056] However, no previous research has been conducted with the objective of using the ESC to produce glass or vitreous materials such as glass frits or glass glazes. Recently, the feasibility of using solar radiation has been investigated concentrated as a sustainable source of energy in a glass production process [SQS Ahmad, RJ Hand, C. Wieckert. Use of concentrated radiation for solar powered glass melting experiments. Solar Energy 109 (2014) 174-182]. The initial experiments of melting a glass within the ternary soda-lime-silica system have shown that rapid and complete conversion of crystalline raw materials to a vitreous, amorphous state is possible according to the X-ray analysis.
    [0057]
    [0058] However, this document discloses experiments of a static or semi-continuous fusion in which a raw material bath is fused, but the process is stopped before the homogenization step in the molten state, without pouring. In this way a bulk glass is obtained, not a glass frit. Another characteristic of the experimental configuration disclosed in this document is the inclusion of a secondary heating around the outlet, provided with an open-tube furnace set at 1200 ° C.
    [0059]
    [0060] The possibility of applying ESC to create a light beam technology to obtain art objects with a glass enamel coating [V. has also been explored. I. Otmakhov. Firing of glass enamel by concentrated solar radiation. Glass and Ceramics, Vol. 72, Nos. 7 - 8, 266-268, (2015)]. However, it is necessary to point out that the last two references mentioned do not use real ESC to achieve the necessary process energy, but, in both cases, a high-flow solar simulator consisting of xenon arc lamps was used as a heat source , whose radiation spectrum is close to the solar spectrum.
    [0061]
    [0062] Additionally, more experiments have been carried out with solar energy of annealing or sintering of silica glass (particles and / or pieces):
    [0063]
    [0064] - Michael Ellestad "solar melting glass melting with fresnel lens";
    [0065] 17- January-2015 XP002773415, URL: http: // youtu .be / xyCH2T5PWUc
    [0066]
    [0067] - Greenpowescience: "" Solar collector of molten glass Fresnel lenses with solar energy "; 07-18-2007, XP002773416
    [0068]
    [0069] URL: http://youtu.be/JG1GfKVoYE
    [0070]
    [0071] Where artists use solar energy to soften small pieces of glass: In Aea Hx "Markus kayser - Solar Sinter Project”; 06-27-2011, XP002773417; URL: http://youtu.be/ptUj8JRAYu8, the artist sinters sand grains.
    [0072]
    [0073] According to the previous paragraphs, there is a need to develop a process in which the real concentrated solar radiation is applied to obtain the energy needed to melt glass frits of different types.
    [0074]
    [0075] BRIEF DESCRIPTION OF THE INVENTION
    [0076]
    [0077] Throughout this description, the following terms are defined as follows:
    [0078] - raw materials: any material that can be used for the manufacture of glass frits such as, but not limited to, silica, alkali / alkaline earth carbonates, alumina, boron oxide, calcium oxide, zirconium oxide, titanium oxide, oxide of lead, zinc oxide, feldspars and combinations thereof.
    [0079]
    [0080] - decarbonation: process by which the raw materials used in the form of carbonate, ie alkaline / alkaline earth carbonates, are broken down to form the corresponding oxides.
    [0081]
    [0082] - fusion: process by which solid raw materials are transformed into liquid phases.
    [0083]
    [0084] - homogenization: process by which the different liquid phases are mixed together to obtain a single liquid mass with equal physicochemical properties throughout the melt.
    [0085]
    [0086] A first object of the present invention is a method for manufacturing glass frits comprising decarbonation, fusion and homogenization of raw materials in which the high power density required is provided by concentrated solar energy. In a preferred embodiment, the raw materials are contained in a crucible, which is heated directly by means of a concentrated beam of sunlight.
    [0087]
    [0088] Raw materials are simultaneously subjected to:
    [0089]
    [0090] decarbonation
    [0091]
    [0092] fusion
    [0093]
    [0094] - homogenization
    [0095] during a period ranging from 15 to 45 min at a temperature measured below the bottom of the crucible above 1400 ° C.
    [0096]
    [0097] The measured temperature could be higher, up to 1800 ° C, depending on the ESC beam.
    [0098]
    [0099] The molten raw material is then poured onto water to cool, thereby forming the glass frit.
    [0100]
    [0101] In a preferred embodiment, the period of time has a range from 7 to 45 minutes, more preferably from 15 to 45 minutes. A further object of the present invention is a device for carrying out said method for manufacturing glass frits, said device comprising:
    [0102]
    [0103] - a flat sun mirror
    [0104]
    [0105] - a solar beam shutter
    [0106]
    [0107] - a solar radiation concentrator
    [0108]
    [0109] - means for storing, feeding and containing raw materials.
    [0110]
    [0111] In a preferred embodiment, the solar radiation concentrator is a parabolic concentrator (1). In a further preferred embodiment:
    [0112] - the means for storing raw materials are a hopper (2)
    [0113]
    [0114] - the means to feed the raw materials are a feeder (3)
    [0115]
    [0116] - the means to contain the raw materials is a crucible (4).
    [0117]
    [0118] Particularly, the crucible (4) is a refractory crucible.
    [0119]
    [0120] The device further comprises a water tank (6) for pouring molten raw materials.
    [0121]
    [0122] Unless otherwise defined, all the technical and scientific terms used have the same meaning as one of those skilled in the art of this invention. Methods and materials similar or equivalent to those described herein may be used in the practice of the present invention.
    [0123] Throughout the description and claims, the word "comprises" and its variations are not intended to exclude other features, elements or stages. Additional objects, advantages and features of the invention will be apparent to those skilled in the art who examine the description or can be learned by the practice of the invention. The following examples and drawings are provided by way of illustrations and are not intended to be limiting of the present invention.
    [0124]
    [0125] BRIEF DESCRIPTION OF THE FIGURES
    [0126]
    [0127] Figure 1: Scheme of the solar installation used to carry out the process of manufacturing frits with concentrated solar energy, in which:
    [0128]
    [0129] 1. Parabolic concentrator
    [0130]
    [0131] 2. Raw materials hopper
    [0132]
    [0133] 3. Raw materials feeder
    [0134]
    [0135] 4. Crucible
    [0136]
    [0137] 5. Crucible crucible arm
    [0138]
    [0139] 6. Water tank with articulated support
    [0140]
    [0141] 7. Sun beam shutter
    [0142]
    [0143] 8. Safety sliding floor
    [0144]
    [0145] 9. Flat mirror
    [0146]
    [0147] Figure 2: Temperature-time records of the experiment to produce glass frits in a solar oven (thermocouple placed in the outer bottom of the crucible) and in an electric oven. Figure 3: X-ray diffraction diagrams (DRX) of the glass frits obtained in solar oven (gray) and electric oven (black).
    [0148] Figure 4: Thermal behavior of glass frits obtained in solar oven (gray) and electric oven (black).
    [0149] Figure 5: Temperature-time records of the experiment to produce glass frits in a solar oven (thermocouple placed in the outer bottom of the crucible) and in an electric oven.
    [0150] The temperature representation in the solar oven extends until the end of the process.
    [0151]
    [0152] DETAILED DESCRIPTION OF THE INVENTION
    [0153]
    [0154] The invention relates to a new method for obtaining glass frits that use concentrated solar energy, which implies several notable advantages compared to traditional processes. Traditional processes carry out the heating of raw materials in a reactor consisting of a crucible where they are heated, decarbonised, melted and homogenized to produce the final product (glass frit). Most of the furnaces used in commercial manufacturing are electric furnaces or furnaces heated by fuels. In both cases there is a huge energy consumption and also a large production of CO2.
    [0155]
    [0156] In the conventional process to produce frits, the raw materials are placed inside a crucible, which is heated from outside to inside. In the present invention (see Figure 1), using a vertical axis solar radiation parabolic concentrator (1), heating is carried out by directing the focus of the concentrated beam directly on the raw material load, inside the crucible (4). Consequently, a great saving in energy consumption will be obtained due to the higher energy density of concentrated solar radiation. In addition, the duration of the process is drastically reduced because the raw materials are under the focus of solar radiation, as soon as the crucible (4) is in an upright position and the shutter (7) is opened. Thus, they begin to heat immediately by the concentrated solar beam from the parabolic concentrator (1). As the power density of this concentrated solar beam is much higher than in traditional furnaces, the heating rate is very high and, consequently, the time to reach the desired reaction temperature is reduced. This invention proposes a new process for the manufacture of frits using a specific solar thermal energy system consisting of a solar installation of vertical axis concentration built to measure according to the characteristics of the process. With this design it is possible to use a very high power density to heat raw materials directly and more quickly to high temperatures. The process includes direct heating of raw materials with concentrated solar energy to increase efficiency in time and energy consumption.
    [0157]
    [0158] Basically, the new frits production process is as follows:
    [0159] 1. - The loading of raw materials into the reactor is introduced, namely a crucible (4) located at the focal point of the parabolic solar concentrator (1), by means of a raw material feeder (3), which a Once the load is finished, it moves to a position outside the parabolic concentrator.
    [0160]
    [0161] 2. - The solar shutter (7) is opened to allow the solar beam to be redirected from the flat mirror (9) to the parabolic concentrator (1).
    [0162]
    [0163] 3. - The high density of solar energy at the focal point produces rapid heating, which leads to decarbonation and simultaneous fusion of raw materials and homogenization of the final melt.
    [0164]
    [0165] 3.- Once the melt reaches the required temperature, it cools quickly by pouring it into a water tank (6) to produce a frit. The pouring is done by means of the tilting arm (5) of the crucible that rotates the crucible (4) to allow the melt to spill.
    [0166] Once the crucible (4) is again in an upright position, it is refilled with a new load of the raw material mixture and the process continues with step "1", while the water tank (6) is moves, by means of the articulated support, to a position outside the parabolic concentrator.
    [0167]
    [0168] With this new process, the time required for heating the raw material, melting, decarbonation and homogenization is extremely short. Consequently, the speed of transformation of raw materials in the final glass is much higher than in traditional processes. As shown in the preferred embodiments, none of the original raw materials are detected in the final frit. Although the process has a shorter duration, the quality of the final product is similar to that of melted frits by a conventional procedure.
    [0169]
    [0170] The process for preparing glass frits according to the present invention has several advantages compared to those using conventional ovens:
    [0171] 1.- Because of the use of solar energy, there is no direct or indirect CO2 emission due to the generation of energy. This is a clear benefit from the point of view of the greenhouse effect. This benefit is very important since the glass frit manufacturing industry is a high consumer of fossil fuels, because high process temperature is required. Even if the ovens are electrically heated there is a hidden fossil fuel consumption because approximately 35% of the electricity is produced with fossil fuels and the efficiency of Production of these plants is around 40%. In addition, losses associated with the transformation and transport of energy must be considered.
    [0172] 2. - The second benefit is that the only cost of this new process is the installation and its maintenance.
    [0173] 3. - The particles of raw materials have an irregular surface that acts as a perfect sink for solar radiation and increases the global heat transfer because there is no reflection. Even if the concentrated solar beams heat a solid surface, as is the case with the crucible wall in gas ovens or electric ovens, the heat losses would be slightly lower. In this way, a reduction of the total energy involved in the process is achieved and there is a better global heat transfer across the surface of the raw materials. Traditional processes require a higher temperature in the outer wall of the crucible. The conduction coefficient of the crucible material controls the heating time because it is always the controlling stage. However, a higher temperature is needed in the outer wall of the crucible to heat the load of raw material inside the crucible. It is well known that an increase in temperature means an increase in cost in any process.
    [0174] 4. - When the grains of raw materials are melted in the upper part of the crucible, the originated liquid phase descends along the pores, heating the grains located in lower layers. This molten liquid falls vertically heating all the grains it finds. Consequently, raw materials that have not reacted heat up more quickly due to the greater surface contact between the molten material and the grain surface. The global transfer of energy is much greater than if the heating were carried out through the crucible walls as in the traditional process, where this effect occurs only near the wall.
    [0175] In addition, the higher power density of the concentrated solar beam increases the global transfer of heat to the raw material load, with a reduction in heating time and the consequent increase in productivity.
    [0176] 5. - Because the load of raw material is directly heated, the outside temperature of the crucible is lower than in traditional processes, it means less heat losses and, consequently, a reduction in the energy consumption of the process. 6. - Regarding the cost of the crucible, traditional processes use materials with high thermal resistance and simultaneously with a high conduction coefficient. Both features mean a higher price. In the present invention, the raw material load is directly heated and the crucible can be manufactured with lower cost insulating refractory material. In addition, there is a very important reduction in mechanical erosion and chemical corrosion of the inner wall of the crucible, increasing its useful life.
    [0177] 7.- The final consequence of these previous advantages is that this new process leads to a reduction of more than 80% in the reaction time (heating, decarbonation and fusion) which means an increase in the productivity of the process.
    [0178]
    [0179] In comparison with the prior art disclosures where solar simulators are used, [S.Q.S. Ahmad, R.J. Hand, C. Wieckert. Use of concentrated radiation for fusion experiments with solar energy. Solar Energy 109 (2014) 174-182], the main differences are the simultaneous decarbonization, fusion and homogenization of raw materials vs. Static or semi-continuous conditions and that there is no need for a secondary heating source. The process of the invention allows to obtain glass frits by means of a continuous one-stage process while the process using the solar simulator ends without pouring, therefore, reproducing a bulk vessel.
    [0180]
    [0181] And in relation to the experiments of the artists, mentioned in the state of the art, the energy required in this process is significantly less than that of a complex glass melting process from batches of raw material as in the present invention.
    [0182]
    [0183] EMBODIMENTS OF THE INVENTION
    [0184]
    [0185] The chemical composition of commercial glass frits includes the combination of several components:
    [0186]
    [0187] -Glass trainers: SiO2, B2O3
    [0188]
    [0189] -Fused oxides: Na2O, K2O, PbO, B2O3, U2O
    [0190]
    [0191] -Stabilizers: CaO, BaO, MgO, PbO, AhO3, ZnO
    [0192]
    [0193] -Opacifiers: ZrO2, SnO2, TiO2
    [0194]
    [0195] - Devitrifying oxides: ZnO, CaO, BaO, MgO, TiO2
    [0196]
    [0197] According to different physical and chemical characteristics, commercial frits are classified into the following six groups:
    [0198] 1- Crystal frits
    [0199] 2- White zirconium fries
    [0200] 3 - Medium fusibility frits, transparent and bright
    [0201] 4- Melting fries
    [0202] 5- Reactive melting frits
    [0203] 6- Matte fries
    [0204] The chemical composition of the different groups is indicated in Table 1.
    [0205]
    [0206] Table 1. Chemical composition range (% by weight) of commercial glass frites White Fused Fuse
    [0207] Flux Crystalline Oxide Matte Zirconium Reactive Medium
    [0208] Alkalines 3-6 3-7 3-7 0-15 - 0-10
    [0209] CaO 4-8 4-8 3-6 0-10 --- 0-20
    [0210] BaO 0-2 0-2 0-2 --- --- ---
    [0211] ZnO 4-8 4-8 3-6 0-5 --- 0-30
    [0212] PbO 0-20 0-10 30-40 0-85 45-69 0-35
    [0213] AhO3 4-8 4-8 2-4 --- --- 0-5
    [0214] B2O3 5-15 10-15 5-10 0-30 20 2-40
    [0215] SiO2 50-60 50-55 40-50 15-50 11-35 30-60
    [0216] ZrO2 --- 7-12 --- --- --- 0-5
    [0217] TiO2 --- --- --- --- --- 0-10
    [0218]
    [0219] For the embodiments of the present invention, glass compositions belonging to five different groups of frits were formulated (Table 1), namely crystalline (C); zirconium white (WZr); medium fusibility (MF); flux (F) and titanium matte (MTi). The compositions of the starting frits are shown in Table 2.
    [0220]
    [0221] Table 2. Initial chemical composition (% by weight) of the investigated glasses.
    [0222]
    [0223] Oxide C WZr MF F MTi
    [0224] SiO2 50 50 40 50 40
    [0225] B2O3 15 15 10 20 20
    [0226] Al2O3 4 4 2 - 2
    [0227]
    [0228] Na2O 3 - 4 10 2
    [0229]
    [0230] K2O - - - 10 -
    [0231]
    [0232] Li2O 3 7 3 - 2
    [0233]
    [0234] CaO 8 4 6 10 2
    [0235]
    [0236] BaO 2 2 2 - 25
    [0237]
    [0238] ZnO 5 8 3 - 7
    [0239]
    [0240] PbO 10 - 30 - -
    [0241]
    [0242] ZrO2 - 10 - - -
    [0243]
    [0244] Theoretical Tusion (° C) 993 1079 822 880 885
    [0245]
    [0246] The raw materials used to obtain the glass frits were silica sand of low iron content, AI2O3 reagent grade, B2O3, ZnO, PbO and ZrÜ2. The alkaline and alkaline earth elements were introduced as reactive grade carbonates. The mixtures were homogenized in a planetary ball mill (TURBULA) for 15 min. For the comparison of the properties of the final frits, the charges were melted in parallel in a vertical axis parabolic solar oven and in a traditional electric oven. In both cases, the compositions were melted in tabular alumina crucibles. Once molten at a specific temperature, the molten liquid was poured into cold water.
    [0247]
    [0248] To carry out the preparation of frits using concentrated solar energy, a parabolic vertical axis solar oven was used.
    [0249]
    [0250] A scheme of the solar installation used for the manufacture of frits with concentrated solar energy is shown in Fig. 1, in which the concentrated solar energy is provided by a flat mirror (9), a solar beam shutter (7) and a parabolic concentrator (1).
    [0251]
    [0252] The raw material is stored in a hopper of raw material (2) and loaded into the crucible (4), placed at the focal point of the concentrated solar beam, by means of a feeder of raw materials (3). Once the load is finished, the raw material feeder (3) moves to a position where it is not damaged by the concentrated solar beam. In addition, no shadow should be caused by the position of this feeder (3).
    [0253]
    [0254] Upon completion of the reaction and melting and to carry out the rapid cooling of the final melt, an articulated support moves a water tank (6) to the proper position in which the melt is poured.
    [0255]
    [0256] The pouring of the melt onto the water for cooling is done using a crucible crucible arm (5) that supports the crucible (4).
    [0257]
    [0258] The installation used was the "Medium Size Solar Furnaces (MSSFs)" of the "CNRS-PROMESS Solar facilities" (Font Romeu-Odeillo, France).
    [0259] The solar oven is a 0.9 kW installation equipped with a 1.5 m diameter parabolic reflector that produces a focal point 15 mm in diameter, with a high power density approx. 1000 W / m2 The incident solar radiation has a shutter placed between the parabolic concentrator and the flat mirror (heliostat). The heliostat follows the path of the sun and reflects the solar radiation vertically to the parabolic concentrator. To measure the temperature at the outer bottom of the crucible, a K type thermocouple was placed.
    [0260]
    [0261] Once the raw materials melted inside the crucible, the melt was kept a few minutes under exposure to solar radiation to allow homogenization and then poured over water to produce the glass frit.
    [0262]
    [0263] For the comparison of the properties of the final frits and the efficiency of the process, the same glass frit compositions were melted in an electric oven. In both cases, the same type and dimensions of the crucible and the same weight of the load were used.
    [0264]
    [0265] Figure 2 shows the thermal cycle followed to obtain the frits in both the solar oven and the electric oven. As can be seen, the use of concentrated solar energy produces a reduction in process time of over 80%, compared to the conventional electric furnace.
    [0266] Figure 5 shows the thermal cycle followed to obtain the frits in both the solar oven and the electric oven. The difference with Figure 2 is that the representation of the temperature in the solar oven has been completed until the end of the process.
    [0267]
    [0268] Characterization of the final frits
    [0269]
    [0270] The results of the characterization of different frits prepared using both the solar concentration oven and the conventional electric oven are shown. The objective of this characterization is to determine if the type of energy, power density and thermal cycle used in the preparation of the frits leads to materials with the same physical-chemical characteristics.
    [0271]
    [0272] The chemical analysis of the resulting glass frits was determined by X-ray fluorescence (FRX) using a Bruker S8 Tiger spectrometer on pressed tablets of powdered glass samples (<63 pm). The determination of B and Li was performed by emission spectrometry with inductive coupling plasma source (ICP-OES) on a Varian 725-ES spectrometer. The evaluation of the amorphous nature of the frits after the fusion was carried out by X-ray diffraction (DRX) using a Bruker D8 Advance device with a Cu Ka radiation, filtered with Ni, at 30 mA and 40 kV. The data were recorded in the range 5-60 ° 20 (step size 0.019732 ° and 0.5 s counting time for each step) .The thermal stability of the glass frits was analyzed by differential thermal analysis (ATD ) on samples of fried frit (<63 pm). The ATD tests were carried out from room temperature to 1200 ° C, at a heating rate of 50 ° C • min-1 in an air atmosphere (100 m Lm in-1) on a TA Instrument device (mod SDT- Q600).
    [0273]
    [0274] Figure 3 shows the DRX diagrams corresponding to frits obtained in both the solar oven and the electric oven. It can be seen that the diffraction profiles of all the frits (except that corresponding to the WZr frit prepared in an electric oven) only show the characteristic amorphous halo of vitreous materials, in which no diffraction peaks due to crystalline phases are detected. However, the diffractogram of the frit with the highest melting temperature (WZr) obtained in the electric furnace shows small diffraction peaks attributable to ZrO2, indicating that this phase did not react completely during the melting process in the electric furnace and it remains as unreacted material in the final glass frit.
    [0275] This is an additional advantage because this new process will allow the fusion of frit compositions with a high content of refractory oxide, which are more difficult to melt in conventional ovens.
    [0276]
    [0277] On the other hand, for each different type of fries, it can be seen that the DRX profiles are very similar. It is noteworthy that, despite the shorter time spent in the new process of fusion with solar energy, the structure of the glass network of the resulting frits is very similar.
    [0278]
    [0279] The chemical composition of the final frits prepared in both solar and electric furnace and determined by FRX and ICP-OES are shown in Table 3. The theoretical initial composition of the raw material mixtures is also included.
    [0280]
    [0281] Table 3. Chemical composition (% by weight) of the frits prepared in both solar and electric ovens.
    [0282]
    [0283] Oxide Composition Oven Oven
    [0284]
    [0285] (% weight) theoretical solar electric
    [0286]
    [0287] Frying flux
    [0288]
    [0289] SiO2 50 47.04 53.72
    [0290]
    [0291]
    [0292]
    [0293] AhO3 0 15.00 2.24
    [0294]
    [0295] Na2O 10 9.07 11.1
    [0296]
    [0297]
    [0298]
    [0299] CaO 10 9.35 10.03
    [0300]
    [0301] White Zirconium Frit
    [0302]
    [0303] SiO2 50 43.47 50.52
    [0304]
    [0305]
    [0306]
    [0307] Al2O3 4 22.5 5.71
    [0308]
    [0309] Li2O 7 3.67 5.13
    [0310]
    [0311] CaO 4 3.34 4.39
    [0312] BaO 2 1.54 2.29 ZnO 8 6.40 8.10 ZrO2 10 8.27 11.25 Crystal Fried
    [0313] YES2 50 50.30 52.60 B2O3 15 9.75 11.80 AI2O3 4 11.50 5.83 Na2O 3 3.60 3.97 L2O 3 1.83 2.59 CaO 8 4.33 4.43 BaO 2 1.91 2.33 ZnO 5 5.27 5.38 PbO 10 10.49 10.05 Medium Fuse Frit
    [0314] SiO2 40 37.88 40.19 B2O3 10 5.84 7.12 Al2O3 2 11.0 3.98 Na2O 4 4.10 4.70 Li2O 3 1.71 2.24 CaO 6 5.80 6.23 BaO 2 1.71 2.24 ZnO 3 3.00 3.16 PbO 30 28.18 29.52 Titanium frit
    [0315] SiO2 40 41.09 41.81 B2O3 20 14.60 15.1 Al2O3 2 7.76 4.02 Na2O 2 2.13 2.65
    [0316]
    [0317] Li2O 2 1.28 1.63
    [0318]
    [0319] ZnO 2 1.69 1.69
    [0320]
    [0321] PbO 25 24.35 25.59
    [0322]
    [0323] TiO2 7 6.44 6.86
    [0324]
    [0325] It can be seen that in the melting process in a conventional electric furnace, the melt causes a high level of corrosion of the crucible wall, as observed by the marked increase in the alumina content in the final frit composition. Thus, alumina is detected even in the frit composition in which alumina was not added to the initial raw material composition. In general, crucible corrosion is higher the lower the melt viscosity, as expected.
    [0326]
    [0327] Losses of B2O3 are also observed by boron volatilization, which are much greater when the melting process is carried out in the electric furnace than when the glass frits are obtained with concentrated solar energy. This result can be attributed to the longer time required for melting in the electric oven. As mentioned above, the use of high power density energy, provided by a solar concentrator, to carry out the manufacture of frits, allows to reduce the process time by approximately 80%, in contrast to the long time required to obtain the same material in a conventional electric oven. The variation of the rest of the components in the frits composition corresponds to the adjustment of the mass balance.
    [0328]
    [0329] Consequently, it can be concluded that the use of concentrated solar energy to make glass frits has additional advantages such as: less corrosion of the crucible wall and less volatilization of boron in the melting process.
    [0330]
    [0331] The thermal behavior of the glass frits was evaluated by ATD. Figure 4 shows the ATD curves of the glass frits produced in both solar and electric furnaces. In general, the curves corresponding to each type of frit show a similar profile, which again shows that despite the shorter time required to complete the melting process in the solar oven, the structure of the final frits obtained by concentrated solar energy must be similar to that of the frits processed in the electric oven. All thermograms show the fall Distinctive endothermic at baseline corresponding to the glass transition temperature (Tg).
    [0332]
    [0333] Table 4 shows the Tg values for the different glass frits. It can be seen that in all cases the glass frits prepared by using concentrated solar energy show values of Tg lower than those corresponding to the frits produced in the electric oven. This result is probably due to the differences observed in glass frits compositions.
    [0334]
    [0335] Table 4. Tg (° C) values of glass frits produced in both solar and electric furnaces
    [0336]
    [0337] Oven MF F MTi C WZr
    [0338]
    [0339] Solar 490 574 501 527 554
    [0340]
    [0341] Electric 552 606 512 553 604
    [0342]
    [0343] As mentioned above, the shorter thermal cycle when the solar oven is used leads to less corrosion of the melt against the walls of the refractory crucibles, thus incorporating low alumina content into the final glass frit composition. In addition, the volatilization of boron is also lower during melting in the solar oven. As a result, the final composition of the glass frits prepared in the solar oven shows a higher content of melting oxides and will lead to lower viscosity liquids and therefore, to lower Tg values. At higher temperatures, the ATD curves show different exothermic bands indicating that subsequent heat treatments of these glass frits could lead to the devitrification of different crystalline phases.
    权利要求:
    Claims (8)
    [1]
    1. - Method for the manufacture of glass frits comprising decarbonation, fusion and homogenization of raw materials in which the high power density required is provided by concentrated solar energy, characterized in that the raw materials contained in a crucible (4) they simultaneously submit to:
    decarbonation
    fusion
    - homogenization
    During a period ranging from 5 to 45 min at a temperature measured below the bottom of the crucible above 1400 ° C and the molten raw materials are subsequently poured onto the water for cooling, thus forming the glass frit.
    [2]
    2. - Method for manufacturing glass frits according to claim 1, wherein the period of time ranges from 7 to 45 min.
    [3]
    3. - Method for manufacturing glass frits according to claim 1, wherein the period of time ranges from 7 to 45 min.
    [4]
    4. - Device for carrying out a method as defined in claims 1 to 3, comprising:
    - a flat sun mirror (9)
    - a sunlight beam shutter (7)
    - a solar radiation concentrator (1)
    - means for storing, feeding and containing raw materials.
    [5]
    5. - Device according to claim 4, wherein the solar radiation concentrator is a parabolic concentrator (1).
    [6]
    6. - Device according to any of claims 4 and 5, wherein:
    - the means for storing raw materials are a hopper (2)
    - the means to feed the raw materials are a feeder (3)
    - the means to contain the raw materials are a crucible (4).
    [7]
    7. Device according to claim 6, wherein the crucible (4) is a refractory crucible.
    [8]
    8. Device according to any one of claims 4 to 7, wherein it also comprises a water tank (6) for pouring molten raw materials
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    同族专利:
    公开号 | 公开日
    ES2732490R1|2019-12-17|
    EP3372561A1|2018-09-12|
    ES2732490B2|2020-05-07|
    WO2018162383A1|2018-09-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN2808897Y|2005-06-30|2006-08-23|广州赛唯热工设备有限公司|Glass kiln solar preheating and residual heat recovery device|
    CN203187515U|2013-04-16|2013-09-11|中建材（镇江）光电应用技术研究院有限公司|High-temperature heating device|
    US9441426B2|2013-05-24|2016-09-13|Oil States Industries, Inc.|Elastomeric sleeve-enabled telescopic joint for a marine drilling riser|
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    优先权:
    申请号 | 申请日 | 专利标题
    EP17382111.7A|EP3372561A1|2017-03-06|2017-03-06|Method and device for manufacturing glass frits|
    PCT/EP2018/055296|WO2018162383A1|2017-03-06|2018-03-05|Method and device for manufacturing glass frits|
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