WO2016051053A1 - Process for manufacturing a solid element made of ceramic material, capable of being used in particular for heat storage - associated solid element - Google Patents
Process for manufacturing a solid element made of ceramic material, capable of being used in particular for heat storage - associated solid element Download PDFInfo
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- WO2016051053A1 WO2016051053A1 PCT/FR2015/052571 FR2015052571W WO2016051053A1 WO 2016051053 A1 WO2016051053 A1 WO 2016051053A1 FR 2015052571 W FR2015052571 W FR 2015052571W WO 2016051053 A1 WO2016051053 A1 WO 2016051053A1
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- substantially equal
- less
- mixture
- temperature
- cooking
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000007787 solid Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 7
- 238000005338 heat storage Methods 0.000 title abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 75
- 239000004927 clay Substances 0.000 claims abstract description 27
- 239000010881 fly ash Substances 0.000 claims abstract description 23
- 239000002956 ash Substances 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 9
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000010411 cooking Methods 0.000 claims description 49
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000003245 coal Substances 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims 4
- 238000010304 firing Methods 0.000 abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 239000011449 brick Substances 0.000 description 32
- 239000006101 laboratory sample Substances 0.000 description 13
- 238000010586 diagram Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011819 refractory material Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 229920001353 Dextrin Polymers 0.000 description 2
- 239000004375 Dextrin Substances 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 235000014755 Eruca sativa Nutrition 0.000 description 1
- 244000024675 Eruca sativa Species 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- -1 T1O2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C04B33/00—Clay-wares
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Definitions
- the present invention relates to a method of manufacturing a solid element made of ceramic material as well as the solid element that can be obtained by this method.
- fly ash is used from the combustion of bituminous coal, which is compressed into granules and then heated to a temperature of 1400 ° C which corresponds to their melting temperature for two hours.
- the above method is expensive to implement because the temperature used for cooking is very high and the cooking time is also relatively long.
- EP 2 045 228 A2 describes a method of manufacturing a refractory material based on water and fly ash and may contain clay.
- WO 201 1/075783 A1 discloses a method of manufacturing solid elements based on fly ash and clay.
- the elements obtained have good mechanical strength and low porosity.
- the proportion of clay is nevertheless quite high, which makes the process expensive.
- WO 2007/126215 relates to a method of manufacturing a building element by extrusion of a cluster of hearth ash and clay and possibly dry coal ash.
- the element obtained has good water absorption properties.
- a first object of the present invention is to propose a novel method of manufacturing a solid element made of a ceramic-type material that can be used in particular for storing heat or as a refractory material for upholstering the interior of furnaces. , for example.
- Another object of the invention is to propose a method of manufacturing a solid element made of a ceramic-type material that can be used in particular for storing heat or as a refractory material for upholstering the inside of ovens that allows to obtain an element having a determined porosity.
- Another object of the present invention is to solve all or part of the technical problems related to the aforementioned prior art.
- Another object of the present invention is to propose a method for manufacturing a solid element made of a ceramic material whose implementation is inexpensive and / or which allows or at least partly a recycling of industrial waste such as, for example, for example, fly ash, especially coal-fired thermal power plant fly ash and / or hearth ashes, especially coal-fired power plant hearth ashes.
- the present invention relates to a method for manufacturing a solid element made of ceramic material, suitable for use in particular for storing heat, according to which
- a base mixture in the form of a powder comprising the following compounds is prepared: SiO 2, Al 2 O 3, TiO 2, Fe 2 O 3, CaO, MgO, Na 2 O and K 2 O
- the mixture obtained is shaped so as to form a green, solid element
- said green element obtained is optionally dried
- said green element optionally dried, is subjected to a maximum cooking temperature substantially equal to or greater than 11 ° C. and substantially equal to or lower than 1200 ° C. so as to consolidate said element;
- said element obtained is allowed to cool to room temperature.
- said base mixture is carried out by mixing fly ash from a coal-fired power plant, coal-fired hearth furnace ashes and clay.
- a base mixture comprising a fly ash fraction of a coal-fired power plant / coal-fired hearth furnace ash is determined, whereby said solid element has a given porosity. It is another merit of the Applicant to have demonstrated that the ratio of fly ash / center of focus mentioned above makes it possible to control the porosity and therefore the density (density) of the element obtained by the process of the invention.
- said mixture contains a quantity of clay equal to 10% of the sum of the masses of said fly ash and said hearth ashes.
- This amount of clay makes the process economical.
- the shaping can be obtained, for example, by molding, casting, pounding, extrusion, pressing or any other known technique.
- the shaping can be implemented by pressing into a matrix, for example metal.
- the pressing can be implemented in a uni axial way.
- the pressure makes it possible to compact the powder formed by the basic mixture. Beyond a certain pressure applied to the base mixture, the energy accumulates in the powder in the form of elastic energy. When relaxing this energy can crack the raw brick.
- a pressure substantially equal to or greater than 30 MPa and substantially equal to or less than 60 MPa is applied to form said element.
- said maximum cooking temperature is substantially equal to 1150 ° C., which makes it possible to obtain cooked elements having a density that is satisfactory for their industrial use, in particular as heat storage elements.
- the cooking makes it possible to sinter the powders of the base mixture.
- Baking allows the creation of ionocovalent bonds between the grains of the powders in order to weld them to each other. This operation makes it possible to densify the basic mixture and to obtain a solid material that can be demolded and handled easily. If the cooking temperature is above 1200 ° C, at least 50% of the components of the basic mixture are in the liquid state; the vitreous phase becomes too great and causes deformations in the solid element obtained. If the maximum cooking temperature is below 1100 ° C, sintering is not effective. In the case of the abovementioned basic mixture according to the invention, the vitreous phase which is likely to be present in the final solid element is composed of SiO 2 and Al 2 O 3 .
- said green element is subjected to said maximum cooking temperature for a duration substantially equal to or greater than 300 min and substantially equal to or less than 480 min, in particular substantially equal to 360 min.
- the time during which the raw element is brought to said maximum cooking temperature depends on the size of the green element.
- said green element, optionally dried is brought to the maximum cooking temperature for a duration substantially equal to or greater than 300 min, in particular substantially equal to 360 min and substantially equal to or less than 480 min. Beyond 480 min, the process is no longer economically profitable.
- a pre-cooking of said element is carried out by heating it to a pre-cooking temperature substantially equal to or greater than 500 ° C. and substantially equal to or lower than 800 ° C., in particular to a substantially equal pre-cooking temperature. at 600 ° C before subjecting said element to said maximum cooking temperature.
- This pre-cooking step is preferably always carried out at the same time as the cooking and takes place during the rise in temperature of the raw element to the cooking temperature.
- This pre-cooking makes it possible to degassing which makes it possible to avoid swelling of the element.
- the duration of said pre-cooking may for example be substantially equal to or greater than 30 min and substantially equal to or less than 120 min, in particular substantially equal to 60 min.
- said element is maintained at a holding temperature substantially equal to or greater than 900 ° C. and substantially equal to or less than 1100 ° C. and in particular substantially equal to 1000 ° C. for a given duration that may be substantially equal to or greater than 300. min and substantially equal to or less than 480 min, after subjecting said element to said maximum cooking temperature.
- This cooling stage makes it possible to control the size of the crystals in the microstructure of the ceramic obtained and to increase the density of the material obtained.
- the heating rate to said cooking temperature is substantially equal to or less than 2 ° C / min and in particular substantially equal to 0.4 ° C / min.
- said base mixture comprises, by weight, 90% or more of 90% fly ash from a coal-fired power plant, which makes it possible to give the fired solid element a specific density, particularly for its use in the storage of heat.
- the clay used is not limited according to the invention. It may be, as an example of RR40 clay as disclosed later, sold by the company Imerys or any other clay or mixture of clays.
- said clay comprises a mass percentage of:
- MgO substantially equal to 0.30.
- the nature of the added liquid is not limited according to the invention.
- water is added to said base mixture and in particular a quantity of water substantially equal to or greater than 5% by weight of the mass of said base mixture and substantially equal to or less than 18% by weight of the mass of said mixture. mixed. It is possible to add a quantity of water substantially equal to 15% by weight of the mass of said mixture.
- the addition of liquid and in particular water makes it possible to improve the efficiency of the pressing step and to increase the flood behavior of the solid elements according to the invention.
- an adjuvant in water such as, for example: methyl ethylene glycol, dextrins, in particular dextrins of the Tackidex® brand marketed by Roquette®, waste originating from the production of paper pulp, or sodium tripolyphosphate.
- This water or other liquid must be extracted from the brick during a drying step that precedes the cooking step. The duration of the drying and its temperature depend on the amount of liquid to be evaporated. In the case of water, the Applicant has demonstrated that an amount of between 5 and 18% by weight of the base mixture optimizes the raw behavior and the shaping step.
- said base mixture comprises in mass percentage a quantity of:
- CaO substantially equal to or greater than 0.5 and substantially equal to or less than 3;
- said base mixture further comprises phosphorus pentoxide and especially a mass percentage of phosphorus pentoxide substantially equal to or greater than 0.005 and substantially equal to or less than 0.25.
- said base mixture has a maximum grain size substantially equal to 1 mm; according to the invention, 95% of the grains have a size less than 160 ⁇ .
- the present invention also relates to a solid element, obtainable by the method according to the invention and which typically comprises, as a percentage by weight, a quantity of:
- CaO substantially equal to or greater than 0.5 and substantially equal to or less than 3;
- - K 2 O substantially equal to or greater than 0.5 and substantially equal to or less than 2.5; and optionally phosphorus pentoxide and especially a mass percentage of phosphorus pentoxide substantially equal to or greater than 0.005 and substantially equal to or less than 0.25.
- This solid element may have a density substantially equal to or greater than 1, 7 and substantially equal to or less than 2.3 t / m 3 .
- It may have an open porosity substantially equal to or greater than 5% and substantially equal to or less than 30%.
- This vitreous phase is composed of S1O2 and Al2O3.
- solid element defines, within the meaning of the present invention, any solid whatever its shape and dimensions. It may be, for example, a pellet, a brick, a sphere, a honeycomb structure. We can favor the known structures that have already been proven in the storage of heat.
- the term "sintering” refers to the process of consolidation by action of the heat of a granular agglomerate more or less compact, with or without fusion of one or more of its constituents, without melting of all components.
- fly ash refers to the finely divided residue resulting from the combustion of pulverized coal. Fly ash is recovered during the dust removal of flue gases from thermal power plants that use crushed coal as fuel in the presence or absence of co-combustible materials. The fly ash is obtained by electrostatic or mechanical precipitation of the powder particles contained in the flue gases of the boilers.
- Their chemical composition may vary; according to the invention, they consist essentially of S1O2, AI2O3, T1O2, Fe2O3, CaO, MgO, Na 2 O and K 2 O. It may also comprise at least one compound / the following: MnO2, SO3, Cl and P2O5.
- hetero ash define the residues of coal combustion recovered directly at the base of the boiler. Their composition may vary; they are essentially or exclusively formed of SiO 2 , Al 2 O 3 , and Fe 2 O 3 .
- open porosity refers to the volume of the cavities communicating with each other.
- the open porosity is measured according to the invention by the vacuum method according to ASTM C329-88 (201 1).
- FIG. 1 represents a first cooking diagram which represents the curve of the temperature of an element according to the invention (laboratory sample size) as a function of time, during its cooking and its subsequent cooling;
- FIG. 2 represents a second cooking diagram which represents the curve of the temperature of an element according to the invention (laboratory sample size) as a function of time, during its cooking and its subsequent cooling
- FIG. 3 represents, for a given composition, the appearance of a cross section of bricks according to the invention (laboratory sample size), obtained with a firing according to the diagram of FIG. 1 (left) and according to the diagram of FIG. 2 (right);
- FIG. 4 represents the density of the element according to the invention (laboratory sample size) as a function of the FCA percentage of the base mixture, each mixture additionally comprising a quantity of clay as mentioned above equal to 10% of the FCA / mixture.
- CBA the cooking being implemented according to the diagram of FIG. 2;
- FIG. 5 shows a photograph taken under an electron microscope of a section of a brick obtained according to the cooking diagram shown in FIG. 2 for an FCA / CBA 100/0 base mixture to which an amount of clay equal to 10% by weight of this mixture was added;
- FIG. 6 shows a photograph taken under an electron microscope of a section of a brick obtained according to the cooking diagram shown in FIG. 2 for an FCA / CBA 70/30 base blend to which an amount of clay equal to 10% by weight of this mixture was added;
- FIG. 7 represents the open porosity in% of the total volume as a function of the firing temperature of the element according to the invention (laboratory sample size).
- FCA aluminosilicone fly ash from the combustion of coal pulverized in a flame power plant at a temperature of 1400 ° C. These ashes are marketed under the name SILICOLINE® Dry by the company Surschiste). These ashes form a powder whose maximum grain diameter is less than 315 ⁇ . These fly ash are called FCA in the rest of this application;
- Dry Silicoline® is used as marketed.
- Silicolit® is marketed at around 15% humidity. In order to facilitate its use, it is dried for 24 hours at 110.degree. C. in an oven and then ground and sieved with a sieve whose meshes have an opening of .mu.m. It is also possible to use screened Silicolit® with a sieve with 5x5mm square mesh.
- RR40 clay is crushed and then sieved with a sieve of ⁇ ⁇ .
- the raw materials in powder form are mixed to form a homogeneous base mixture.
- a quantity of water corresponding to 6% of the total mass of the base mixture is then added for the laboratory samples.
- a sample is put in an oven during
- FCA Component Mixture
- FCA 100 70 50 30 0 CBA 0 30 50 70 100
- the amount of clay indicated in Table I makes it possible to obtain a density of the order of 1. 58 g / cm 3 .
- the density is lower and the mixture does not make it possible to shape a green element having sufficient cohesion.
- the use of too much clay increases the production cost of the material.
- the mixtures obtained are pre-compacted and then pressed into a mold of rectangular section of dimensions 1 15mmx65mm (laboratory sample size). A pressure of 34 MPa is then applied using a hydraulic press. Each mold contains a quantity of mixture equal to 400g. This gives a brick 20 mm high which is a laboratory sample. Bricks of industrial dimensions of 30 mm in thickness are also produced by pressing in a mold of dimensions 230x1 14 mm exerting a pressure of 30 MPa. The bricks obtained have a weight of 1, 4kg. In the case of these bricks of industrial size, was added to the base mixture a quantity of water substantially equal to 15% by weight of the base mixture.
- the raw industrial bricks obtained are dried in an oven at 100 ° C for 12 hours, 24 or 48 hours after their manufacture, whether for laboratory samples or industrial-sized bricks.
- the cooking is carried out in an electric furnace for laboratory samples or a gas tunnel kiln for larger bricks.
- Table III below groups together the results obtained in terms of density and open porosity as a function of the firing temperature, the heating rate for each of the blends in Table I. Some compositions were used for the production of industrial bricks as mentioned above. . The values corresponding to these industrial bricks are shown in Table III below and are indicated in parentheses.
- FIG. 1 represents the curve of the temperature as a function of time during cooking and after the latter, for the first series
- FIG. 2 represents the curve of the temperature as a function of time during cooking and after this last for the second series.
- the temperature increases linearly from 20 ° C to 1150 ° C over a period of 753.33 minutes, which equates to a heating rate of 1.5 ° C / min.
- the temperature is then kept constant at 1150 ° C for 60 min.
- the temperature then drops to 20 ° C in 376 minutes.
- the temperature increases linearly from 20 ° C to 600 ° C in 386.66 min which corresponds to a heating rate of 1.5 ° C / min.
- the temperature then remains at 600 ° C. for 60 min and then increases linearly up to 1150 ° C. in 366 min.
- the temperature then remains at 1150 ° C for 60 min.
- the temperature then drops to 1000 ° C in 50 minutes.
- the temperature is then kept constant and equal to 1000 ° C. for 60 min. It is then let down to 20 ° C as in the case of the curve shown in FIG. 1.
- FIG. 3 shows a sectional view of the bricks obtained (laboratory sample size), the bricks of the first series being on the left in FIG. 3 and that obtained for the second series on the right. It can be seen in FIG. 3 that the temperature curve of FIG. 2 allows to obtain flat bricks and perfectly homogeneous. The bricks obtained with the cooking curve of FIG. 1 are swollen on the top or have pockets of air, making them unusable. The same results were obtained for other base blend compositions.
- Raw bricks obtained from base mixtures of varied composition but still containing 10% by weight of clay as mentioned above relative to the mass of FCA + CBA were cooked according to the cooking diagram shown in FIG. 2.
- the density of the baked bricks thus obtained was then measured according to the method of Archimedes.
- the results obtained are grouped together in FIG. 4.
- the results grouped together in FIG. 4 indicate that the higher the amount of FCA, the higher the density.
- FIG. 5 is an electron microscope view of a section of a brick obtained according to the cooking diagram shown in FIG. 2 for a mixture of base FCA / CBA 100/0 to which was added 10% by mass of this mixture, of clay as aforesaid.
- FIG. 5 there is a high concentration of SiO 2 -Al 2 O 3 and grains rich in Fe 2 O 3 as well as some porosity.
- FIG. 6 is an electron microscope view of a section of a brick obtained according to the cooking diagram shown in FIG. 2 for an FCA / CBA 70/30 base mixture to which was added 10% by weight of this mixture, clay as mentioned above.
- FIG. 6 there is also a high concentration of S102-Al2O3 and Fe2O3-rich grains and a higher porosity than in the case of FIG. 5 and the appearance of a network connecting the different cavities.
- FIG. 7 shows that the higher the cooking temperature, the lower the open porosity.
- a rate of rise in temperature substantially equal to 0.4 ° C / min is adequate. There is no need to pre-cook.
- the step of maintaining at a holding temperature for a period of 300 minutes to 480 minutes is important to obtain bricks having a shape suitable for their industrial use, without swelling and having a satisfactory density.
- the holding temperature is then substantially equal to 1000 ° C.
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Abstract
The present invention relates to a process for manufacturing a solid element made of ceramic material, capable of being used in particular for heat storage, according to which: - a base mixture in powder form is produced that comprises the following compounds: SiO2, Al2O3, TiO2, Fe2O3, CaO, MgO, Na2O and K2O; - at least one liquid is added; - the mixture obtained is shaped after addition of liquid to form a solid green element; - said green element obtained is optionally dried; - said optionally dried green element is subjected to a firing temperature substantially equal to or greater than 1110°C and substantially equal to or less than 1200°C so as to consolidate said element; and - said fired element is left to cool down to ambient temperature. Characteristically, according to the invention, said base mixture is produced by mixing fly ash from a coal-fired power plant, furnace ash from a coal-fired power plant and clay.
Description
PROCEDE DE FABRICATION D'UN ELEMENT SOLIDE EN MATERIAU DE TYPE CERAMIQUE, APTE A ETRE UTILISE NOTAMMENT POUR LE STOCKAGE DE LA CHALEUR-ELEMENT SOLIDE ASSOCIE DOMAINE TECHNIQUE METHOD FOR MANUFACTURING A SOLID ELEMENT OF CERAMIC MATERIAL, SUITABLE FOR USE IN PARTICULAR FOR THE STORAGE OF HEAT-SOLID ELEMENT ASSOCIATED WITH TECHNICAL FIELD
La présente invention concerne un procédé de fabrication d'un élément solide en matériau de type céramique ainsi que l'élément solide susceptible d'être obtenu par ce procédé. The present invention relates to a method of manufacturing a solid element made of ceramic material as well as the solid element that can be obtained by this method.
ART ANTERIEUR PRIOR ART
L'article intitulé "utilization of coal-ash minerais for technological ceramics" publié dans la revue "Journal of Materials Science (n°27, 1992, page 1781 à 1784) décrit un procédé de fabrication d'une vitrocéramique. Selon ce procédé, on utilise des cendres volantes, provenant de la combustion de charbon bitumineux. Ces cendres sont compressées en granulés puis chauffées jusqu'à une température de 1400°C qui correspond à leur température de fusion pendant deux heures. The article entitled "Use of Coal-ash Minerals for Ceramics" published in the journal "Journal of Materials Science" (No. 27, 1992, page 1781 to 1784) describes a method of manufacturing a glass-ceramic. fly ash is used from the combustion of bituminous coal, which is compressed into granules and then heated to a temperature of 1400 ° C which corresponds to their melting temperature for two hours.
Le procédé précité est coûteux à mettre en œuvre car la température utilisée pour la cuisson est très élevée et le temps de cuisson est également relativement long. The above method is expensive to implement because the temperature used for cooking is very high and the cooking time is also relatively long.
Le document EP 2 045 228 A2 décrit un procédé de fabrication d'un matériau réfractaire à base d'eau et de cendres volantes et pouvant contenir de l'argile. EP 2 045 228 A2 describes a method of manufacturing a refractory material based on water and fly ash and may contain clay.
Le document WO 201 1/075783 A1 décrit un procédé de fabrication d'éléments solides à base de cendres volantes et d'argile. Les éléments obtenus présentent une bonne résistance mécanique et une faible porosité. La proportion d'argile est néanmoins assez élevée ce qui rend le procédé coûteux. WO 201 1/075783 A1 discloses a method of manufacturing solid elements based on fly ash and clay. The elements obtained have good mechanical strength and low porosity. The proportion of clay is nevertheless quite high, which makes the process expensive.
Le document WO 2007/126215 concerne un procédé de fabrication d'un élément de construction par extrusion d'un agrégat de cendres de foyer et d'argile et éventuellement des cendres de charbon sèches. L'élément obtenu possède de bonnes propriétés d'absorption de l'eau. WO 2007/126215 relates to a method of manufacturing a building element by extrusion of a cluster of hearth ash and clay and possibly dry coal ash. The element obtained has good water absorption properties.
L'article intitulé «Fly ash of minerai coal as ceramic tiles raw material » publié dans la revue Science directe le 15 mars 2006 page 59 à 68 préconise
d'ajouter à un mélange d'argile et de cendres volantes du feldspath afin d'obtenir une porosité fermée. En effet, en fonction de l'utilisation de l'élément solide obtenu, la porosité de ce dernier revêt une importance particulière. Une porosité trop importante fragilise le matériau mais le rend léger et lui confère des propriétés d'isolant thermique. L'ajout de feldspath permet effectivement de contrôler la porosité mais rend le procédé coûteux et peu écologique. The article entitled "Fly ash of mineral coal as ceramic tiles raw material" published in the journal Science direct March 15, 2006 page 59 to 68 advocates add to a mixture of clay and fly ash feldspar to obtain a closed porosity. Indeed, depending on the use of the solid element obtained, the porosity of the latter is of particular importance. Too much porosity weakens the material but makes it light and gives it thermal insulation properties. The addition of feldspar effectively controls the porosity but makes the process expensive and unecological.
OBJET DE L'INVENTION OBJECT OF THE INVENTION
Un premier but de la présente invention est de proposer un nouveau procédé de fabrication d'un élément solide en matériau de type céramique, apte à être utilisé notamment pour le stockage de la chaleur ou en tant que matériau réfractaire pour tapisser l'intérieur des fours, par exemple. A first object of the present invention is to propose a novel method of manufacturing a solid element made of a ceramic-type material that can be used in particular for storing heat or as a refractory material for upholstering the interior of furnaces. , for example.
Un autre but de l'invention est de proposer un procédé de fabrication d'un élément solide en matériau de type céramique, apte à être utilisé notamment pour le stockage de la chaleur ou en tant que matériau réfractaire pour tapisser l'intérieur des fours qui permette d'obtenir un élément présentant une porosité déterminée. Another object of the invention is to propose a method of manufacturing a solid element made of a ceramic-type material that can be used in particular for storing heat or as a refractory material for upholstering the inside of ovens that allows to obtain an element having a determined porosity.
Un autre but de la présente invention est de résoudre tout ou partie des problèmes techniques liés à l'art antérieur précité. Another object of the present invention is to solve all or part of the technical problems related to the aforementioned prior art.
Un autre but de la présente invention est de proposer un procédé de fabrication d'un élément solide en matériau de type céramique dont la mise en œuvre soit peu coûteuse et/ou qui permet ou moins en partie un recyclage de déchets industriels tels que, par exemple, les cendres volantes, notamment les cendres volantes de centrale thermique à charbon et/ou les cendres de foyers, notamment les cendres de foyer de centrale thermique à charbon. Another object of the present invention is to propose a method for manufacturing a solid element made of a ceramic material whose implementation is inexpensive and / or which allows or at least partly a recycling of industrial waste such as, for example, for example, fly ash, especially coal-fired thermal power plant fly ash and / or hearth ashes, especially coal-fired power plant hearth ashes.
RESUME DE L'INVENTION SUMMARY OF THE INVENTION
La présente invention concerne un procédé de fabrication d'un élément solide en matériau de type céramique, apte à être utilisé notamment pour le stockage de la chaleur, selon lequel The present invention relates to a method for manufacturing a solid element made of ceramic material, suitable for use in particular for storing heat, according to which
on réalise un mélange de base sous forme de poudre comprenant les composés suivants : S1O2, AI2O3, T1O2, Fe2O3, CaO, MgO, Na2O et K2O a base mixture in the form of a powder comprising the following compounds is prepared: SiO 2, Al 2 O 3, TiO 2, Fe 2 O 3, CaO, MgO, Na 2 O and K 2 O
on ajoute au moins un liquide,
on met en forme le mélange obtenu de façon à former un élément cru, solide ; at least one liquid is added, the mixture obtained is shaped so as to form a green, solid element;
on fait éventuellement sécher ledit élément cru obtenu ; said green element obtained is optionally dried;
on soumet ledit élément cru éventuellement séché à une température maximale de cuisson sensiblement égale ou supérieure à 1 1 10°C et sensiblement égale ou inférieure à 1200C de manière à consolider ledit élément; et said green element, optionally dried, is subjected to a maximum cooking temperature substantially equal to or greater than 11 ° C. and substantially equal to or lower than 1200 ° C. so as to consolidate said element; and
on laisse ledit élément obtenu refroidir jusqu'à la température ambiante. said element obtained is allowed to cool to room temperature.
De manière caractéristique, selon l'invention, on réalise ledit mélange de base en mélangeant des cendres volantes de centrale thermique à charbon, des cendres de foyer de centrale thermique à charbon et de l'argile. Typically, according to the invention, said base mixture is carried out by mixing fly ash from a coal-fired power plant, coal-fired hearth furnace ashes and clay.
C'est en effet le mérite de la Demanderesse que d'avoir montré qu'il était possible de fabriquer un matériau solide avec le mélange précité. Ce mélange permet de recycler des cendres de foyer et des cendres volantes qui sont des déchets potentiellement toxiques si elles sont laissées à l'air libre ou même enterrées. It is indeed the merit of the Applicant to have shown that it was possible to manufacture a solid material with the above mixture. This mixture recycles fireplace ashes and fly ash that are potentially toxic waste if left in the open air or even buried.
La Demanderesse a en effet mis en évidence qu'il était possible de fabriquer des éléments solides avec une température de cuisson inférieure à celle décrite en référence à l'art antérieur. Cette température de cuisson plus basse permet de rendre le procédé plus économique et également plus respectueux de l'environnement. The Applicant has indeed demonstrated that it was possible to manufacture solid elements with a firing temperature lower than that described with reference to the prior art. This lower cooking temperature makes the process more economical and also more environmentally friendly.
Avantageusement, on réalise un mélange de base comprenant une fraction cendres volantes de centrale thermique à charbon/cendres de foyer de centrale thermique à charbon déterminée, moyennant quoi ledit élément solide présente une porosité donnée. C'est un autre mérite de la Demanderesse que d'avoir mis en évidence que le ratio cendres volantes/centre de foyer précité permet de contrôler la porosité et donc la masse volumique (densité) de l'élément obtenu par le procédé de l'invention. Advantageously, a base mixture comprising a fly ash fraction of a coal-fired power plant / coal-fired hearth furnace ash is determined, whereby said solid element has a given porosity. It is another merit of the Applicant to have demonstrated that the ratio of fly ash / center of focus mentioned above makes it possible to control the porosity and therefore the density (density) of the element obtained by the process of the invention.
De préférence, ledit mélange contient une quantité d'argile égale à 10% de la somme des masses desdites cendres volantes et desdites cendres de foyer. Cette quantité d'argile rend le procédé économique.
La mise en forme peut être obtenue, par exemple, par moulage, coulage, pilonnage, extrusion, pressage ou toute autre technique connue. La mise en forme peut être mise en œuvre par pressage dans une matrice, par exemple métallique. Le pressage peut être mis en œuvre de manière uni axiale. La pression permet de compacter la poudre formée par le mélange de base. Au-delà d'une certaine pression appliquée au mélange de base, l'énergie s'accumule dans la poudre sous forme d'énergie élastique. Lors de la détente cette énergie peut fissurer la brique crue. Avantageusement, une pression sensiblement égale ou supérieure à 30MPa et sensiblement égale ou inférieure à 60 MPa est appliquée pour former ledit élément. Preferably, said mixture contains a quantity of clay equal to 10% of the sum of the masses of said fly ash and said hearth ashes. This amount of clay makes the process economical. The shaping can be obtained, for example, by molding, casting, pounding, extrusion, pressing or any other known technique. The shaping can be implemented by pressing into a matrix, for example metal. The pressing can be implemented in a uni axial way. The pressure makes it possible to compact the powder formed by the basic mixture. Beyond a certain pressure applied to the base mixture, the energy accumulates in the powder in the form of elastic energy. When relaxing this energy can crack the raw brick. Advantageously, a pressure substantially equal to or greater than 30 MPa and substantially equal to or less than 60 MPa is applied to form said element.
Avantageusement, ladite température maximale de cuisson est sensiblement égale à 1 150°C, ce qui permet d'obtenir des éléments cuits présentant une densité satisfaisante pour leur utilisation industrielle, en particulier comme éléments de stockage de la chaleur. Advantageously, said maximum cooking temperature is substantially equal to 1150 ° C., which makes it possible to obtain cooked elements having a density that is satisfactory for their industrial use, in particular as heat storage elements.
Bien que la Demanderesse ne soit pas liée à une telle explication, il semble que la cuisson permet de réaliser le frittage des poudres du mélange de base. La cuisson permet de créer des liaisons ionocovalentes entre les grains des poudres afin de les souder les uns aux autres. Cette opération permet de densifier le mélange de base et d'obtenir un matériau solide qui peut être démoulé et manipulé facilement. Si la température de cuisson est supérieure à 1200°C, au moins 50% des composants du mélange de base sont à l'état liquide ; la phase vitreuse devient trop importante et engendre des déformations dans l'élément solide obtenu. Si la température maximale de cuisson est inférieure à 1 100°C, le frittage n'est pas efficace. Dans le cas du mélange de base précité selon l'invention, la phase vitreuse qui est susceptible d'être présente dans l'élément solide final est composée de S1O2 et d'AI2O3. Although the Applicant is not bound to such an explanation, it seems that the cooking makes it possible to sinter the powders of the base mixture. Baking allows the creation of ionocovalent bonds between the grains of the powders in order to weld them to each other. This operation makes it possible to densify the basic mixture and to obtain a solid material that can be demolded and handled easily. If the cooking temperature is above 1200 ° C, at least 50% of the components of the basic mixture are in the liquid state; the vitreous phase becomes too great and causes deformations in the solid element obtained. If the maximum cooking temperature is below 1100 ° C, sintering is not effective. In the case of the abovementioned basic mixture according to the invention, the vitreous phase which is likely to be present in the final solid element is composed of SiO 2 and Al 2 O 3 .
Avantageusement, on soumet ledit élément cru éventuellement séché à ladite température maximale de cuisson pendant une durée sensiblement égale ou supérieure à 300 min et sensiblement égale ou inférieure à 480 min, en particulier sensiblement égale à 360 min. La durée pendant laquelle l'élément cru est porté à ladite température maximale de cuisson dépend de la taille de l'élément cru. Pour un élément cru ayant la taille d'une brique
industrielle telle que définie dans la partie expérimentale de la présente demande, on porte ledit élément cru, éventuellement séché à la température maximale de cuisson pendant une durée sensiblement égale ou supérieure à 300min, en particulier sensiblement égale à 360 min et sensiblement égale ou inférieure à 480 min. Au-delà de 480 min, le procédé n'est plus économiquement rentable. Advantageously, said green element, optionally dried, is subjected to said maximum cooking temperature for a duration substantially equal to or greater than 300 min and substantially equal to or less than 480 min, in particular substantially equal to 360 min. The time during which the raw element is brought to said maximum cooking temperature depends on the size of the green element. For a raw element that is the size of a brick As defined in the experimental part of the present application, said green element, optionally dried, is brought to the maximum cooking temperature for a duration substantially equal to or greater than 300 min, in particular substantially equal to 360 min and substantially equal to or less than 480 min. Beyond 480 min, the process is no longer economically profitable.
Selon un mode de réalisation, on réalise une pré cuisson dudit élément en le chauffant à une température de pré cuisson sensiblement égale ou supérieure à 500°C et sensiblement égale ou inférieure à 800°C, en particulier à une température de pré cuisson sensiblement égale à 600°C avant de soumettre ledit élément à ladite température maximale de cuisson. Cette étape de pré-cuisson est de préférence toujours mise en œuvre en même temps que la cuisson et prend place lors de la montée en température de l'élément cru jusqu'à la température de cuisson. Cette pré-cuisson permet de réaliser un dégazage qui permet d'éviter les gonflements de l'élément. La durée de ladite pré cuisson peut être par exemple sensiblement égale ou supérieure à 30min et sensiblement égale ou inférieure à 120 min, en particulier sensiblement égale à 60 min. According to one embodiment, a pre-cooking of said element is carried out by heating it to a pre-cooking temperature substantially equal to or greater than 500 ° C. and substantially equal to or lower than 800 ° C., in particular to a substantially equal pre-cooking temperature. at 600 ° C before subjecting said element to said maximum cooking temperature. This pre-cooking step is preferably always carried out at the same time as the cooking and takes place during the rise in temperature of the raw element to the cooking temperature. This pre-cooking makes it possible to degassing which makes it possible to avoid swelling of the element. The duration of said pre-cooking may for example be substantially equal to or greater than 30 min and substantially equal to or less than 120 min, in particular substantially equal to 60 min.
Avantageusement, on maintient ledit élément à une température de maintien sensiblement égale ou supérieure à 900°C et sensiblement égale ou inférieure à 1 100°C et en particulier sensiblement égale à 1000°C pendant une durée donnée pouvant être sensiblement égale ou supérieure à 300 min et sensiblement égale ou inférieure à 480 min, après avoir soumis ledit élément à la dite température maximale de cuisson. Ce palier de refroidissement permet de contrôler la taille des cristaux dans la microstructure de la céramique obtenue et d'augmenter la densité du matériau obtenu. Advantageously, said element is maintained at a holding temperature substantially equal to or greater than 900 ° C. and substantially equal to or less than 1100 ° C. and in particular substantially equal to 1000 ° C. for a given duration that may be substantially equal to or greater than 300. min and substantially equal to or less than 480 min, after subjecting said element to said maximum cooking temperature. This cooling stage makes it possible to control the size of the crystals in the microstructure of the ceramic obtained and to increase the density of the material obtained.
Avantageusement, la vitesse de chauffe jusqu'à ladite température de cuisson est sensiblement égale ou inférieure à 2°C/min et notamment sensiblement égale à 0,4°C/min. Une telle vitesse de chauffe ou vitesse de montée en température permet une meilleure homogénéisation des températures dans le four et dans les pièces à cuire, ce qui limite les phénomènes de gonflement précités.
Avantageusement, ledit mélange de base comprend en masse 90% ou plus de 90% de cendres volantes de centrale à charbon, ce qui permet de conférer à l'élément solide cuit une densité adaptée en particulier pour son utilisation dans le stockage de la chaleur. Advantageously, the heating rate to said cooking temperature is substantially equal to or less than 2 ° C / min and in particular substantially equal to 0.4 ° C / min. Such a heating rate or rate of rise in temperature makes it possible to better homogenize the temperatures in the oven and in the rooms to be cooked, which limits the aforementioned swelling phenomena. Advantageously, said base mixture comprises, by weight, 90% or more of 90% fly ash from a coal-fired power plant, which makes it possible to give the fired solid element a specific density, particularly for its use in the storage of heat.
L'argile utilisée n'est pas limitée selon l'invention. Il peut s'agir, à titre d'exemple d'argile RR40 comme exposé ultérieurement, commercialisée par la société Imérys ou de toute autre argile ou mélange d'argiles. The clay used is not limited according to the invention. It may be, as an example of RR40 clay as disclosed later, sold by the company Imerys or any other clay or mixture of clays.
Selon un mode de réalisation particulier, ladite argile comprend un pourcentage massique de : According to a particular embodiment, said clay comprises a mass percentage of:
- S1O2 sensiblement égal ou supérieur à 55 et sensiblement égal ou inférieur à 56 et notamment sensiblement égal à 55.90 - S1O2 substantially equal to or greater than 55 and substantially equal to or less than 56 and in particular substantially equal to 55.90
- AI2O3 sensiblement égale ou supérieur à 38 et notamment sensiblement égal à 38,50 ; - Al2O3 substantially equal to or greater than 38 and in particular substantially equal to 38.50;
- Fe2O3 sensiblement inférieur ou égal à 2,60 et notamment sensiblement égal à 2.00 ; - Fe2O3 substantially less than or equal to 2.60 and in particular substantially equal to 2.00;
- ΤΊΟ2 sensiblement égal à 2.50 - ΤΊΟ2 substantially equal to 2.50
- K2O sensiblement égal à 0.10 K 2 O substantially equal to 0.10
- Na2Û sensiblement égal à 0.05 Na2O substantially equal to 0.05
- CaO sensiblement égal à 0.65 ; et CaO substantially equal to 0.65; and
- MgO sensiblement égal à 0.30. MgO substantially equal to 0.30.
La nature du liquide ajouté n'est pas limitée selon l'invention. De préférence, on ajoute de l'eau audit mélange de base et notamment une quantité d'eau sensiblement égale ou supérieure à 5% en masse de la masse dudit mélange de base et sensiblement égale ou inférieure à 18% en masse de la masse dudit mélange. On peut ajouter une quantité d'eau sensiblement égale à 15% en masse de la masse dudit mélange. L'ajout de liquide et notamment d'eau permet d'améliorer l'efficacité de l'étape de pressage et d'augmenter la tenue à crue des éléments solide selon l'invention. On peut également ajouter un adjuvant dans l'eau, comme par exemple : le méthyl éthylène glycol, des dextrines, notamment des dextrines de la marque Tackidex® commercialisées par la société Roquette®, des déchets provenant de la production de la pâte à papier, ou du tripolyphosphate de sodium.
Cette eau ou autre liquide devra être extraite de la brique lors d'une étape de séchage qui précède, l'étape de cuisson. La durée du séchage et sa température sont fonction de la quantité de liquide à évaporer. Dans le cas de l'eau, la Demanderesse a mis en évidence qu'une quantité comprise entre 5 et 18 % en masse du mélange de base permet d'optimiser la tenue à cru et l'étape de mise en forme. The nature of the added liquid is not limited according to the invention. Preferably, water is added to said base mixture and in particular a quantity of water substantially equal to or greater than 5% by weight of the mass of said base mixture and substantially equal to or less than 18% by weight of the mass of said mixture. mixed. It is possible to add a quantity of water substantially equal to 15% by weight of the mass of said mixture. The addition of liquid and in particular water makes it possible to improve the efficiency of the pressing step and to increase the flood behavior of the solid elements according to the invention. It is also possible to add an adjuvant in water, such as, for example: methyl ethylene glycol, dextrins, in particular dextrins of the Tackidex® brand marketed by Roquette®, waste originating from the production of paper pulp, or sodium tripolyphosphate. This water or other liquid must be extracted from the brick during a drying step that precedes the cooking step. The duration of the drying and its temperature depend on the amount of liquid to be evaporated. In the case of water, the Applicant has demonstrated that an amount of between 5 and 18% by weight of the base mixture optimizes the raw behavior and the shaping step.
Par ailleurs, la Demanderesse a mis en évidence que le séchage doit s'opérer lentement et dans toute l'épaisseur de l'élément cru. Des températures de séchage comprises entre 40°C et 100°C ou égales à 40°C ou 100°C ont été identifiés comme adéquates. Moreover, the Applicant has shown that the drying must take place slowly and throughout the thickness of the raw element. Drying temperatures between 40 ° C and 100 ° C or equal to 40 ° C or 100 ° C have been identified as adequate.
Avantageusement, ledit mélange de base comprend en pourcentage massique une quantité de : Advantageously, said base mixture comprises in mass percentage a quantity of:
- S1O2 sensiblement égale ou supérieure à 48 et sensiblement égale ou inférieure à 62 ; - S1O2 substantially equal to or greater than 48 and substantially equal to or less than 62;
- AI2O3 sensiblement égale ou supérieure à 25 et sensiblement égale ou inférieure à 32 ; - Al 2 O3 substantially equal to or greater than 25 and substantially equal to or less than 32;
- ΤΊΟ2 sensiblement égale ou supérieure à 0,5 et sensiblement égale ou inférieure à 1 ,5 ; - ΤΊΟ2 substantially equal to or greater than 0.5 and substantially equal to or less than 1, 5;
- Fe2O3 sensiblement égale ou supérieure à 8 et sensiblement égale ou inférieure à 9 ; - Fe2O3 substantially equal to or greater than 8 and substantially equal to or less than 9;
- CaO sensiblement égale ou supérieure à 0,5 et sensiblement égale ou inférieure à 3 ; CaO substantially equal to or greater than 0.5 and substantially equal to or less than 3;
- MgO sensiblement égale ou supérieure à 0,5 et sensiblement égale ou inférieure à 3 ; - MgO substantially equal to or greater than 0.5 and substantially equal to or less than 3;
- Na2Û sensiblement égale ou supérieure à 0,1 et sensiblement égale ou inférieure à 0,8 ; - Na2O substantially equal to or greater than 0.1 and substantially equal to or less than 0.8;
- K2O sensiblement égale ou supérieure à 0,5 et sensiblement égale ou inférieure à 2,5. - K 2 O substantially equal to or greater than 0.5 and substantially equal to or less than 2.5.
Avantageusement, ledit mélange de base comprend, en outre du pentoxide de phosphore et notamment un pourcentage massique de pentoxyde de phosphore sensiblement égal ou supérieur à 0,005 et sensiblement égal ou inférieure à 0,25.
Avantageusement ledit mélange de base présente une taille maximale de grain sensiblement égale 1 mm ; selon l'invention, 95% des grains ont une taille inférieure à 160μηη. Advantageously, said base mixture further comprises phosphorus pentoxide and especially a mass percentage of phosphorus pentoxide substantially equal to or greater than 0.005 and substantially equal to or less than 0.25. Advantageously, said base mixture has a maximum grain size substantially equal to 1 mm; according to the invention, 95% of the grains have a size less than 160μηη.
La présente invention concerne également un élément solide, susceptible d'être obtenu par le procédé selon l'invention et qui, de manière caractéristique, comprend, en pourcentage massique, une quantité de : The present invention also relates to a solid element, obtainable by the method according to the invention and which typically comprises, as a percentage by weight, a quantity of:
- S1O2 sensiblement égale ou supérieure à 48 et sensiblement égale ou inférieure à 62 ; - S1O2 substantially equal to or greater than 48 and substantially equal to or less than 62;
- AI2O3 sensiblement égale ou supérieure à 25 et sensiblement égale ou inférieure à 32 ; - Al2O3 substantially equal to or greater than 25 and substantially equal to or less than 32;
- ΤΊΟ2 sensiblement égale ou supérieure à 0,5 et sensiblement égale ou inférieure à 1 ,5 ; - ΤΊΟ2 substantially equal to or greater than 0.5 and substantially equal to or less than 1, 5;
- Fe2O3 sensiblement égale ou supérieure à 8 et sensiblement égale ou inférieure à 9 ; - Fe2O3 substantially equal to or greater than 8 and substantially equal to or less than 9;
- CaO sensiblement égale ou supérieure à 0,5 et sensiblement égale ou inférieure à 3 ; CaO substantially equal to or greater than 0.5 and substantially equal to or less than 3;
- MgO sensiblement égale ou supérieure à 0,5 et sensiblement égale ou inférieure à 3 ; - MgO substantially equal to or greater than 0.5 and substantially equal to or less than 3;
- Na2Û sensiblement égale ou supérieure à 0,1 et sensiblement égale ou inférieure à 0,8 ; - Na2O substantially equal to or greater than 0.1 and substantially equal to or less than 0.8;
- K2O sensiblement égale ou supérieure à 0,5 et sensiblement égale ou inférieure à 2,5 ; et éventuellement du pentoxide de phosphore et notamment un pourcentage massique de pentoxyde de phosphore sensiblement égal ou supérieur à 0,005 et sensiblement égal ou inférieur à 0,25. - K 2 O substantially equal to or greater than 0.5 and substantially equal to or less than 2.5; and optionally phosphorus pentoxide and especially a mass percentage of phosphorus pentoxide substantially equal to or greater than 0.005 and substantially equal to or less than 0.25.
Cet élément solide peut présenter une densité sensiblement égale ou supérieure à 1 ,7 et sensiblement égale ou inférieure à 2,3 t/m3. This solid element may have a density substantially equal to or greater than 1, 7 and substantially equal to or less than 2.3 t / m 3 .
Il peut présenter une porosité ouverte sensiblement égale ou supérieure à 5% et sensiblement égale ou inférieure à 30%. It may have an open porosity substantially equal to or greater than 5% and substantially equal to or less than 30%.
Il peut également présenter une phase vitreuse qui peut être supérieure à 50% en volume. Cette phase vitreuse est composée de S1O2 et AI2O3. It may also have a glassy phase which may be greater than 50% by volume. This vitreous phase is composed of S1O2 and Al2O3.
DEFINITIONS
Le terme «élément solide» définit, au sens de la présente invention, tout solide quelle que soit sa forme et ses dimensions. Il peut s'agir, par exemple, d'une pastille, d'une brique, d'une sphère, d'une structure en nid d'abeille. On peut privilégier les structures connues qui ont déjà fait leurs preuves dans le stockage de la chaleur. DEFINITIONS The term "solid element" defines, within the meaning of the present invention, any solid whatever its shape and dimensions. It may be, for example, a pellet, a brick, a sphere, a honeycomb structure. We can favor the known structures that have already been proven in the storage of heat.
Le terme « frittage » désigne le processus de consolidation par action de la chaleur d'un agglomérat granulaire plus ou moins compact, avec ou sans fusion d'un ou de plusieurs de ses constituants, sans fusion de la totalité des composants. The term "sintering" refers to the process of consolidation by action of the heat of a granular agglomerate more or less compact, with or without fusion of one or more of its constituents, without melting of all components.
Les termes «cendres volantes de centrale à flamme à charbon» désignent le résidu finement divisé résultant de la combustion du charbon pulvérisé. Les cendres volantes sont récupérées lors du dépoussiérage des fumées rejetées par les centrales thermiques qui utilisent du charbon broyé comme combustible en présence ou non de matériaux de co-combustibles. Les cendres volantes sont obtenues par précipitation électrostatique ou mécanique des particules pulvérulentes contenues dans les gaz de fumée des chaudières. Leur composition chimique peut varier ; selon l'invention, elles sont essentiellement formées de S1O2, AI2O3, T1O2, Fe2O3, CaO, MgO, Na2Û et K2O. Elles peuvent également comprendre au moins un des composés/éléments suivants : MnO2, SO3, Cl et P2O5. The term "coal-fired power plant fly ash" refers to the finely divided residue resulting from the combustion of pulverized coal. Fly ash is recovered during the dust removal of flue gases from thermal power plants that use crushed coal as fuel in the presence or absence of co-combustible materials. The fly ash is obtained by electrostatic or mechanical precipitation of the powder particles contained in the flue gases of the boilers. Their chemical composition may vary; according to the invention, they consist essentially of S1O2, AI2O3, T1O2, Fe2O3, CaO, MgO, Na 2 O and K 2 O. It may also comprise at least one compound / the following: MnO2, SO3, Cl and P2O5.
Les termes «cendres de foyer» définissent les résidus de la combustion de charbon récupérés directement à la base de la chaudière. Leur composition peut varier ; elles sont essentiellement ou exclusivement formées de SiO2, AI2O3, et Fe2O3. The terms "hearth ash" define the residues of coal combustion recovered directly at the base of the boiler. Their composition may vary; they are essentially or exclusively formed of SiO 2 , Al 2 O 3 , and Fe 2 O 3 .
Les termes « porosité ouverte » font référence au volume des cavités communiquant les unes avec les autres. La porosité ouverte est mesurée, selon l'invention par la méthode sous vide selon la norme ASTM C329 - 88(201 1 ). The term "open porosity" refers to the volume of the cavities communicating with each other. The open porosity is measured according to the invention by the vacuum method according to ASTM C329-88 (201 1).
BREVE DESCRIPTION DES FIGURES BRIEF DESCRIPTION OF THE FIGURES
La présente invention sera mieux comprise à la lecture des exemples de réalisation qui suivent et qui font référence aux figures annexées parmi lesquelles
- la FIG. 1 représente un premier diagramme de cuisson qui représente la courbe de la température d'un élément selon l'invention (taille échantillon de laboratoire) en fonction du temps, lors de sa cuisson et de son refroidissement ultérieur ; The present invention will be better understood on reading the examples which follow and which refer to the appended figures, among which FIG. 1 represents a first cooking diagram which represents the curve of the temperature of an element according to the invention (laboratory sample size) as a function of time, during its cooking and its subsequent cooling;
- la FIG. 2 représente un deuxième diagramme de cuisson qui représente la courbe de la température d'un élément selon l'invention (taille échantillon de laboratoire) en fonction du temps, lors de sa cuisson et de son refroidissement ultérieur FIG. 2 represents a second cooking diagram which represents the curve of the temperature of an element according to the invention (laboratory sample size) as a function of time, during its cooking and its subsequent cooling
- la FIG. 3 représente, pour une composition donnée, l'aspect d'une coupe transversale de briques selon l'invention (taille échantillon de laboratoire), obtenues avec une cuisson selon le diagramme de la FIG. 1 (à gauche) et selon le diagramme de la FIG. 2 (à droite) ; FIG. 3 represents, for a given composition, the appearance of a cross section of bricks according to the invention (laboratory sample size), obtained with a firing according to the diagram of FIG. 1 (left) and according to the diagram of FIG. 2 (right);
- la FIG. 4 représente la densité de l'élément selon l'invention (taille échantillon de laboratoire) en fonction du pourcentage en FCA du mélange de base, chaque mélange comportant en plus une quantité d'argile telle que précitée égale à 10% du mélange FCA/CBA, la cuisson étant mise en œuvre selon le diagramme de la FIG. 2 ; FIG. 4 represents the density of the element according to the invention (laboratory sample size) as a function of the FCA percentage of the base mixture, each mixture additionally comprising a quantity of clay as mentioned above equal to 10% of the FCA / mixture. CBA, the cooking being implemented according to the diagram of FIG. 2;
- la FIG. 5 représente une photographie prise au microscope électronique d'une coupe d'une brique obtenue selon le diagramme de cuisson représenté sur la FIG. 2 pour un mélange de base FCA/CBA 100/0 auquel on a ajouté une quantité d'argile égale à 10% en masse de ce mélange ; FIG. 5 shows a photograph taken under an electron microscope of a section of a brick obtained according to the cooking diagram shown in FIG. 2 for an FCA / CBA 100/0 base mixture to which an amount of clay equal to 10% by weight of this mixture was added;
- la FIG. 6 représente une photographie prise au microscope électronique d'une coupe d'une brique obtenue selon le diagramme de cuisson représenté sur la FIG. 2 pour un mélange de base FCA/CBA 70/30 auquel on a ajouté une quantité d'argile égale à 10% en masse de ce mélange ; et FIG. 6 shows a photograph taken under an electron microscope of a section of a brick obtained according to the cooking diagram shown in FIG. 2 for an FCA / CBA 70/30 base blend to which an amount of clay equal to 10% by weight of this mixture was added; and
- la FIG. 7 représente la porosité ouverte en % du volume total en fonction de la température de cuisson de l'élément selon l'invention (taille échantillon de laboratoire). FIG. 7 represents the open porosity in% of the total volume as a function of the firing temperature of the element according to the invention (laboratory sample size).
DESCRIPTION DETAILLEE DE L'INVENTION DETAILED DESCRIPTION OF THE INVENTION
EXEMPLES EXAMPLES
Fabrication de briques
Les matières premières utilisées sont : Brick making The raw materials used are:
- des cendres volantes silico-alumineuses issues de la combustion de houille pulvérisée en centrale à flamme à une température de 1400°C. Ces cendres sont commercialisées sous le nom de SILICOLINE® Sèche par la société Surschiste). Ces cendres forment une poudre dont le diamètre maximal des grains est inférieur à 315μηη. Ces cendres volantes sont dénommées FCA dans la suite de la présente demande ; - aluminosilicone fly ash from the combustion of coal pulverized in a flame power plant at a temperature of 1400 ° C. These ashes are marketed under the name SILICOLINE® Dry by the company Surschiste). These ashes form a powder whose maximum grain diameter is less than 315μηη. These fly ash are called FCA in the rest of this application;
- des cendres de foyers de type silico alumineuses, produites par la combustion de charbon pulvérisé dans les chaudières des centrales thermoélectriques à flamme et commercialisées sous le nom de SILICOLIT ® par la société Surschiste. Ces cendres sont tamisées avec un tamis présentant des mailles formant des ouvertures carrées de dimensions 4x4mm. Elles sont dénommées CBA dans la suite de la présente demande ; et ashes of silico-aluminous type foci produced by the combustion of pulverized coal in the boilers of the thermoelectric flame plants and marketed under the name SILICOLIT® by the company Surschiste. These ashes are sieved with a sieve having meshes forming square openings of dimensions 4x4mm. They are called CBA in the remainder of this application; and
- de l'argile RR40 commercialisée par la société Imerys et broyée de manière à obtenir des grains de taille maximale sensiblement égale à 2mm (TV2); RR40 clay marketed by Imerys and ground to obtain grains of maximum size substantially equal to 2 mm (TV2);
Préparation du mélange de base Preparation of the basic mixture
La Silicoline® sèche est utilisée telle que commercialisée. Dry Silicoline® is used as marketed.
La Silicolit® est commercialisée à environ 15% d'humidité. Afin de faciliter son emploi, elle est séchée pendant 24 h à 1 10°C dans une étuve puis broyée et tamisée avec un tamis dont les mailles présentent une ouverture de Ι ΟΟμιτι. Il est également possible d'utiliser de la Silicolit® tamisée avec un tamis présentant des mailles carrées de dimensions 5x5mm. Silicolit® is marketed at around 15% humidity. In order to facilitate its use, it is dried for 24 hours at 110.degree. C. in an oven and then ground and sieved with a sieve whose meshes have an opening of .mu.m. It is also possible to use screened Silicolit® with a sieve with 5x5mm square mesh.
L'argile RR40 est broyée puis tamisée avec un tamis de Ι ΟΟμιτι. RR40 clay is crushed and then sieved with a sieve of Ι ΟΟμιτι.
Les matières premières sous forme de poudre sont mélangées de manière à former un mélange de base homogène. On ajoute ensuite une quantité d'eau correspondant à 6% de la masse totale du mélange de base pour les échantillons de laboratoire. Un échantillon est mis à l'étuve pendant The raw materials in powder form are mixed to form a homogeneous base mixture. A quantity of water corresponding to 6% of the total mass of the base mixture is then added for the laboratory samples. A sample is put in an oven during
1/2 heure à 100°C pour contrôler le taux d'humidité. 1/2 hour at 100 ° C to control the humidity.
On réalise les mélanges suivants indiqués dans le tableau I: The following mixtures are carried out indicated in Table I:
Tableau I Table I
Mélange (FCA(g)/CBA(g)) 100/0 70/30 50/50 30/70 0/100 Mixture (FCA (g) / CBA (g)) 100/0 70/30 50/50 30/70 0/100
FCA 100 70 50 30 0
CBA 0 30 50 70 100FCA 100 70 50 30 0 CBA 0 30 50 70 100
RR40 10 10 10 10 10 RR40 10 10 10 10 10
La composition chimique calculée de chacun des mélanges précités est indiquée dans le Tableau II suivant : The calculated chemical composition of each of the aforementioned mixtures is indicated in the following Table II:
Tableau II Table II
La quantité d'argile indiquée dans le Tableau I permet d'obtenir une densité de l'ordre de 1 ,58g/cm3. Lorsque la quantité d'argile est plus faible, la densité est moindre et le mélange ne permet pas de façonner un élément cru présentant une cohésion suffisante. Par ailleurs, l'utilisation d'une trop grande quantité d'argile augmente le coût de production du matériau. The amount of clay indicated in Table I makes it possible to obtain a density of the order of 1. 58 g / cm 3 . When the amount of clay is lower, the density is lower and the mixture does not make it possible to shape a green element having sufficient cohesion. In addition, the use of too much clay increases the production cost of the material.
Fabrication de l'élément solide cru Manufacture of the raw solid element
Les mélanges obtenus sont pré-compactés puis pressés dans un moule de section rectangulaire de dimensions 1 15mmx65mm (taille échantillon de laboratoire). On applique alors une pression de 34MPa à l'aide d'une presse hydraulique. Chaque moule contient une quantité de mélange égale à 400g. On obtient ainsi une brique de 20 mm de hauteur qui constitue un échantillon de laboratoire.
On réalise également des briques de dimensions industrielles de 30 mm d'épaisseur, par pressage dans un moule de dimension 230x1 14mm en exerçant une pression de 30MPa. Les briques obtenues présentent un poids de 1 ,4kg. Dans le cas de ces briques de dimensions industrielles, on a jouté au mélange de base une quantité d'eau sensiblement égale à 15% en masse du mélange de base. The mixtures obtained are pre-compacted and then pressed into a mold of rectangular section of dimensions 1 15mmx65mm (laboratory sample size). A pressure of 34 MPa is then applied using a hydraulic press. Each mold contains a quantity of mixture equal to 400g. This gives a brick 20 mm high which is a laboratory sample. Bricks of industrial dimensions of 30 mm in thickness are also produced by pressing in a mold of dimensions 230x1 14 mm exerting a pressure of 30 MPa. The bricks obtained have a weight of 1, 4kg. In the case of these bricks of industrial size, was added to the base mixture a quantity of water substantially equal to 15% by weight of the base mixture.
Les briques industrielles crues obtenues sont séchées dans une étuve à 100°C pendant 12 heures, 24 ou 48h après leur fabrication, que ce soit pour les échantillons de laboratoire ou les briques de taille industrielle. The raw industrial bricks obtained are dried in an oven at 100 ° C for 12 hours, 24 or 48 hours after their manufacture, whether for laboratory samples or industrial-sized bricks.
Cuisson baking
La cuisson est mise en œuvre dans un four électrique pour les échantillons de laboratoire ou un four tunnel à gaz pour les briques de taille plus importante. Le Tableau III suivant regroupe les résultats obtenus en termes de densité et de porosité ouverte en fonction de la température de cuisson, de la vitesse de chauffe pour chacun des mélanges du Tableau I Certaines compositions ont été utilisées pour la production de briques industrielles telles que précitées. Les valeurs correspondant à ces briques industrielles figurent dans le Tableau III ci-dessous et sont indiquées entre parenthèses. The cooking is carried out in an electric furnace for laboratory samples or a gas tunnel kiln for larger bricks. Table III below groups together the results obtained in terms of density and open porosity as a function of the firing temperature, the heating rate for each of the blends in Table I. Some compositions were used for the production of industrial bricks as mentioned above. . The values corresponding to these industrial bricks are shown in Table III below and are indicated in parentheses.
Tableau III Table III
Les valeurs de densité indiquées dans le Tableau III précité sont obtenues par la méthode d'Archimède.
Influence de la vitesse de chauffe sur l'aspect de la brique cuite (échantillons de laboratoire) The density values indicated in the aforementioned Table III are obtained by the method of Archimedes. Influence of the heating rate on the appearance of the baked brick (laboratory samples)
Pour la composition 100/0, on a testé l'influence de la vitesse de chauffe. On a réalisé une série de briques crues identiques conformément au protocole indique précédemment. Les briques obtenues sont des échantillons de laboratoire et ont été divisées en deux séries. La première série a été cuite à 1 175°C For the 100/0 composition, the influence of the heating rate was tested. A series of identical green bricks was made in accordance with the previously mentioned protocol. The bricks obtained are laboratory samples and have been divided into two series. The first series was cooked at 1,175 ° C
La FIG. 1 représente la courbe de la température en fonction du temps lors de la cuisson et après cette dernière, pour la première série, tandis que la FIG. 2 représente la courbe de la température en fonction du temps lors de la cuisson et après cette dernière pour la deuxième série. FIG. 1 represents the curve of the temperature as a function of time during cooking and after the latter, for the first series, while FIG. 2 represents the curve of the temperature as a function of time during cooking and after this last for the second series.
Comme représenté sur la FIG. 1 , pour la première série, la température croît linéairement de 20°C à 1 150°C sur une durée de 753,33 min, ce qui équivaut à une vitesse de chauffe de 1 ,5°C/min. La température est ensuite gardée constante à 1 150°C durant 60 min. La température chute ensuite jusqu'à 20°C en 376 minutes. As shown in FIG. 1, for the first series, the temperature increases linearly from 20 ° C to 1150 ° C over a period of 753.33 minutes, which equates to a heating rate of 1.5 ° C / min. The temperature is then kept constant at 1150 ° C for 60 min. The temperature then drops to 20 ° C in 376 minutes.
Pour la deuxième série, comme représenté sur la FIG. 2, la température augmente de manière linéaire de 20°C à 600°C en 386,66 min ce qui correspond à une vitesse de chauffe de 1 ,5°C/min. La température reste ensuite égale à 600°C pendant 60 min puis augmente linéairement jusqu' à 1 150°C en 366 min. La température reste ensuite égale à 1 150°C durant 60 min. La température redescend ensuite jusqu'à 1000°C en 50 min. La température est alors maintenue constante et égale à 1000°C pendant 60 min. On la laisse ensuite redescendre jusqu'à 20°C comme dans le cas de la courbe représentée sur la FIG. 1 . For the second series, as shown in FIG. 2, the temperature increases linearly from 20 ° C to 600 ° C in 386.66 min which corresponds to a heating rate of 1.5 ° C / min. The temperature then remains at 600 ° C. for 60 min and then increases linearly up to 1150 ° C. in 366 min. The temperature then remains at 1150 ° C for 60 min. The temperature then drops to 1000 ° C in 50 minutes. The temperature is then kept constant and equal to 1000 ° C. for 60 min. It is then let down to 20 ° C as in the case of the curve shown in FIG. 1.
La FIG. 3 montre une vue en coupe des briques obtenues (taille échantillon de laboratoire), les briques de la première série étant à gauche sur la FIG. 3 et celle obtenues pour la deuxième série à droite. On constate sur la FIG. 3 que la courbe de température de la FIG. 2 permet d'obtenir des briques plates et parfaitement homogènes. Les briques obtenues avec la courbe de cuisson de la FIG. 1 sont gonflées sur le dessus ou présentent des poches d'air, les rendant inutilisables.
Les mêmes résultats ont été obtenus pour d'autres compositions de mélange de base. FIG. 3 shows a sectional view of the bricks obtained (laboratory sample size), the bricks of the first series being on the left in FIG. 3 and that obtained for the second series on the right. It can be seen in FIG. 3 that the temperature curve of FIG. 2 allows to obtain flat bricks and perfectly homogeneous. The bricks obtained with the cooking curve of FIG. 1 are swollen on the top or have pockets of air, making them unusable. The same results were obtained for other base blend compositions.
Influence de la composition chimique du mélange de base sur la porosité ouverte Influence of the chemical composition of the basic mixture on open porosity
Des briques crues obtenues à partie de mélanges de base de composition variées mais contenant toujours 10% en masse d'argile telle que précitée par rapport à la masse de FCA+CBA ont été cuites selon le diagramme de cuisson représenté sur la FIG. 2. On a ensuite mesuré la densité des briques cuites ainsi obtenus selon la méthode d'Archimède. Les résultats obtenus sont regroupés sur la FIG. 4. Les résultats regroupés sur la FIG. 4 indiquent que plus la quantité de FCA est élevée, plus la densité augmente. Raw bricks obtained from base mixtures of varied composition but still containing 10% by weight of clay as mentioned above relative to the mass of FCA + CBA were cooked according to the cooking diagram shown in FIG. 2. The density of the baked bricks thus obtained was then measured according to the method of Archimedes. The results obtained are grouped together in FIG. 4. The results grouped together in FIG. 4 indicate that the higher the amount of FCA, the higher the density.
Ces résultats sont corroborés par les images obtenues à l'aide d'un microscope à balayage électronique modèle Philips XL 30: La FIG. 5 est une vue au microscope électronique d'une coupe d'une brique obtenue selon le diagramme de cuisson représenté sur la FIG. 2 pour un mélange de base FCA/CBA 100/0 auquel on a ajouté 10% en masse de ce mélange, d'argile telle que précitée. Sur la FIG. 5, on constate une forte concentration de S1O2- AI2O3 et des grains riches en Fe2Û3 ainsi qu'une certaine porosité. These results are corroborated by the images obtained using a Philips XL 30 scanning electron microscope: FIG. 5 is an electron microscope view of a section of a brick obtained according to the cooking diagram shown in FIG. 2 for a mixture of base FCA / CBA 100/0 to which was added 10% by mass of this mixture, of clay as aforesaid. In FIG. 5, there is a high concentration of SiO 2 -Al 2 O 3 and grains rich in Fe 2 O 3 as well as some porosity.
La FIG. 6 est une vue au microscope électronique d'une coupe d'une brique obtenue selon le diagramme de cuisson représenté sur la FIG. 2 pour un mélange de base FCA/CBA 70/30 auquel on a ajouté 10% en masse de ce mélange, d'argile telle que précitée. Sur la FIG. 6, on constate également une forte concentration de S1O2-AI2O3 et des grains riches en Fe2Û3 ainsi qu'une porosité plus importante que dans le cas de la FIG. 5 et l'apparition d'un réseau reliant les différentes cavités. FIG. 6 is an electron microscope view of a section of a brick obtained according to the cooking diagram shown in FIG. 2 for an FCA / CBA 70/30 base mixture to which was added 10% by weight of this mixture, clay as mentioned above. In FIG. 6, there is also a high concentration of S102-Al2O3 and Fe2O3-rich grains and a higher porosity than in the case of FIG. 5 and the appearance of a network connecting the different cavities.
Influence de la température de cuisson sur la porosité ouverte Influence of cooking temperature on open porosity
On a réalisé comme précédemment indiqué des briques crues avec un mélange de base (à indiquer). Les briques crues ont été cuites selon la courbe de température de la FIG. 2 mais avec des températures de cuisson différentes. Les résultats obtenus sont regroupés sur la FIG. 7. La FIG. 7 montre que plus la température de cuisson est élevée plus la porosité ouverte diminue.
Concernant les briques de taille industrielle, il a été observé qu'il est important d'avoir une faible vitesse de montée en température. Une vitesse de montée en température sensiblement égale à 0,4°C/min est adéquate. Il n'est pas nécessaire de procéder à une pré-cuisson. En revanche, l'étape de maintien à une température de maintien durant une durée de 300 min à 480 min est importante pour obtenir des briques présentant une forme adaptée à leur utilisation industrielle, sans gonflement et ayant une densité satisfaisante. La température de maintien est alors sensiblement égale à 1000°C.
As previously indicated, raw bricks were made with a base mixture (to be indicated). The raw bricks were fired according to the temperature curve of FIG. 2 but with different cooking temperatures. The results obtained are grouped together in FIG. 7. FIG. 7 shows that the higher the cooking temperature, the lower the open porosity. For industrial sized bricks, it has been observed that it is important to have a low rate of temperature rise. A rate of rise in temperature substantially equal to 0.4 ° C / min is adequate. There is no need to pre-cook. In contrast, the step of maintaining at a holding temperature for a period of 300 minutes to 480 minutes is important to obtain bricks having a shape suitable for their industrial use, without swelling and having a satisfactory density. The holding temperature is then substantially equal to 1000 ° C.
Claims
1 . Procédé de fabrication d'un élément solide en matériau de type céramique, apte à être utilisé notamment pour le stockage de la chaleur, selon lequel 1. A method of manufacturing a solid element made of ceramic material, suitable for use in particular for storing heat, according to which
on réalise un mélange de base sous forme de poudre comprenant les composés suivants : S1O2, AI2O3, T1O2, Fe2O3, CaO, MgO, Na2O et K2O a base mixture in the form of a powder comprising the following compounds is prepared: SiO 2, Al 2 O 3, TiO 2, Fe 2 O 3, CaO, MgO, Na 2 O and K 2 O
on ajoute au moins un liquide, at least one liquid is added,
- on met en forme le mélange obtenu de façon à former un élément cru, solide ; the mixture obtained is shaped so as to form a green, solid element;
on fait éventuellement sécher ledit élément cru obtenu ; said green element obtained is optionally dried;
on soumet ledit élément cru éventuellement séché à une température maximale de cuisson sensiblement égale ou supérieure à 1 1 10°C et sensiblement égale ou inférieure à 1200C de manière à consolider ledit élément; et said green element, optionally dried, is subjected to a maximum cooking temperature substantially equal to or greater than 11 ° C. and substantially equal to or lower than 1200 ° C. so as to consolidate said element; and
- on laisse ledit élément obtenu refroidir jusqu'à la température ambiante, said element obtained is allowed to cool to ambient temperature,
caractérisé en ce que l'on réalise ledit mélange de base en mélangeant des cendres volantes de centrale thermique à charbon, des cendres de foyer de centrale thermique à charbon et de l'argile. characterized in that said base mixture is made by mixing fly ash from a coal-fired power station, coal-fired power plant hearth and clay.
2. Procédé selon la revendication 1 , caractérisé en ce que qu'on réalise un mélange de base comprenant une fraction cendres volantes de centrale thermique à charbon/cendres de foyer de centrale thermique à charbon déterminé, moyennant quoi ledit élément solide présente une porosité donnée. 2. Process according to claim 1, characterized in that a basic mixture comprising a fly ash fraction of a coal-fired power plant / coal-fired hearth combustion center ash, whereby said solid element has a given porosity, is produced. .
3. Procédé selon l'une quelconque des revendications 1 et 2, caractérisé en ce que ledit mélange contient une quantité d'argile égale à 10% de la somme des masses desdites cendres volantes et desdites cendres de foyer.3. Method according to any one of claims 1 and 2, characterized in that said mixture contains a quantity of clay equal to 10% of the sum of the masses of said fly ash and said hearth ashes.
4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que ladite température maximale de cuisson est sensiblement égale à 1 150°C. 4. Method according to any one of the preceding claims, characterized in that said maximum cooking temperature is substantially equal to 1150 ° C.
5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'on soumet ledit élément à ladite température maximale
de cuisson pendant une durée sensiblement égale ou supérieure à 300 min et sensiblement égale ou inférieure à 480 min et en particulier sensiblement égale à 360min. 5. Method according to any one of the preceding claims, characterized in that said element is subjected to said maximum temperature cooking for a period substantially equal to or greater than 300 min and substantially equal to or less than 480 min and in particular substantially equal to 360 min.
6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'on réalise une pré cuisson dudit élément en le chauffant à une température de pré cuisson sensiblement égale ou supérieure à 500°C et sensiblement égale ou inférieure à 800°C, en particulier à une température de pré cuisson sensiblement égale à 600°C pendant une durée de pré cuisson donnée, avant de le soumettre à ladite température maximale. 6. Process according to any one of the preceding claims, characterized in that a pre-cooking of said element is carried out by heating it to a pre-cooking temperature substantially equal to or greater than 500 ° C. and substantially equal to or less than 800 ° C. C, in particular at a pre-cooking temperature substantially equal to 600 ° C for a given pre-cooking time, before subjecting it to said maximum temperature.
7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que après avoir soumis ledit élément à ladite température maximale de cuisson, on maintient ledit élément à une température de maintien sensiblement égale ou supérieure à 900°C et sensiblement égale ou inférieure à 1 100°C et en particulier sensiblement égale à 1000°C pendant une durée donnée avant de laisser ledit élément refroidir jusqu'à la température ambiante. 7. Method according to any one of the preceding claims, characterized in that after subjecting said element to said maximum cooking temperature, said element is maintained at a holding temperature substantially equal to or greater than 900 ° C and substantially equal to or less than at 1100 ° C and in particular substantially equal to 1000 ° C for a given time before allowing said element to cool to room temperature.
8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la vitesse de chauffe jusqu'à ladite température maximale de cuisson est sensiblement égale ou inférieure à 2°C/min et notamment sensiblement égale à 0,4°C/min. 8. Method according to any one of the preceding claims, characterized in that the heating rate to said maximum cooking temperature is substantially equal to or less than 2 ° C / min and in particular substantially equal to 0.4 ° C / min.
9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que ledit mélange de base comprend en masse 90% ou plus de 90% de cendres volantes de centrale à charbon. 9. Method according to any one of the preceding claims, characterized in that said base mixture comprises in mass 90% or more than 90% of fly ash coal plant.
10. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que ladite argile comprend un pourcentage massique de : 10. Method according to any one of the preceding claims, characterized in that said clay comprises a mass percentage of:
S1O2 sensiblement égal ou supérieur à 55 et sensiblement égal ou inférieur à 56 et notamment sensiblement égal à 55.90 S1O2 substantially equal to or greater than 55 and substantially equal to or less than 56 and in particular substantially equal to 55.90
AI2O3 sensiblement égale ou supérieur à 38 et notamment sensiblement égal à 38,50 ; AI2O3 substantially equal to or greater than 38 and in particular substantially equal to 38.50;
- Fe2O3 sensiblement inférieur ou égal à 2,60 et notamment sensiblement égal à 2.00 ; - Fe2O3 substantially less than or equal to 2.60 and in particular substantially equal to 2.00;
ΤΊΟ2 sensiblement égal à 2.50 ΤΊΟ2 substantially equal to 2.50
K2O sensiblement égal à 0.10
Na2Û sensiblement égal à 0.05 K 2 O substantially equal to 0.10 Na2O substantially equal to 0.05
CaO sensiblement égal à 0.65 ; et CaO substantially equal to 0.65; and
MgO sensiblement égal à 0.30. MgO substantially equal to 0.30.
1 1 . Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'on ajoute de l'eau audit mélange de base et notamment une quantité d'eau sensiblement égale ou supérieure à 5% en masse de la masse dudit mélange de base et sensiblement égale ou inférieure à 18 % en masse de la masse dudit mélange, en particulier sensiblement égale à 15%. 1 1. Process according to any one of the preceding claims, characterized in that water is added to said base mixture and in particular a quantity of water substantially equal to or greater than 5% by weight of the mass of said base mixture and substantially equal to or less than 18% by weight of the mass of said mixture, in particular substantially equal to 15%.
12. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que ledit mélange de base comprend en pourcentage massique une quantité de : 12. Method according to any one of the preceding claims, characterized in that said base mixture comprises in percentage by mass a quantity of:
- S1O2 sensiblement égale ou supérieure à 48 et sensiblement égale ou inférieure à 62 ; - S1O2 substantially equal to or greater than 48 and substantially equal to or less than 62;
- AI2O3 sensiblement égale ou supérieure à 25 et sensiblement égale ou inférieure à 32 ; - Al 2 O3 substantially equal to or greater than 25 and substantially equal to or less than 32;
- ΤΊΟ2 sensiblement égale ou supérieure à 0,5 et sensiblement égale ou inférieure à 1 ,5 ; - ΤΊΟ2 substantially equal to or greater than 0.5 and substantially equal to or less than 1, 5;
- Fe2O3 sensiblement égale ou supérieure à 8 et sensiblement égale ou inférieure à 9 ; - Fe2O3 substantially equal to or greater than 8 and substantially equal to or less than 9;
- CaO sensiblement égale ou supérieure à 0,5 et sensiblement égale ou inférieure à 3 ; CaO substantially equal to or greater than 0.5 and substantially equal to or less than 3;
- MgO sensiblement égale ou supérieure à 0,5 et sensiblement égale ou inférieure à 3 ; - MgO substantially equal to or greater than 0.5 and substantially equal to or less than 3;
- Na2Û sensiblement égale ou supérieure à 0,1 et sensiblement égale ou inférieure à 0,8 ; - Na2O substantially equal to or greater than 0.1 and substantially equal to or less than 0.8;
- K2O sensiblement égale ou supérieure à 0,5 et sensiblement égale ou inférieure à 2,5. - K 2 O substantially equal to or greater than 0.5 and substantially equal to or less than 2.5.
13. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que ledit mélange de base comprend, en outre du pentoxide de phosphore et notamment un pourcentage massique de pentoxyde de phosphore sensiblement égal ou supérieur à 0,005 et sensiblement égal ou inférieure à 0,25.
13. Method according to any one of the preceding claims, characterized in that said base mixture further comprises phosphorus pentoxide and in particular a mass percentage of phosphorus pentoxide substantially equal to or greater than 0.005 and substantially equal to or less than 0. 25.
14. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que ledit mélange de base présente une taille maximale sensiblement égale à 1 mm. 14. Method according to any one of the preceding claims, characterized in that said basic mixture has a maximum size substantially equal to 1 mm.
15. Elément solide susceptible d'être obtenu par le procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il comprend, en pourcentage massique, une quantité de : 15. Solid element obtainable by the process according to any one of the preceding claims, characterized in that it comprises, in mass percentage, a quantity of:
- S1O2 sensiblement égale ou supérieure à 48 et sensiblement égale ou inférieure à 62 ; - S1O2 substantially equal to or greater than 48 and substantially equal to or less than 62;
- AI2O3 sensiblement égale ou supérieure à 25 et sensiblement égale ou inférieure à 32 ; - Al2O3 substantially equal to or greater than 25 and substantially equal to or less than 32;
- ΤΊΟ2 sensiblement égale ou supérieure à 0,5 et sensiblement égale ou inférieure à 1 ,5 ; - ΤΊΟ2 substantially equal to or greater than 0.5 and substantially equal to or less than 1, 5;
- Fe2O3 sensiblement égale ou supérieure à 8 et sensiblement égale ou inférieure à 9 ; - Fe2O3 substantially equal to or greater than 8 and substantially equal to or less than 9;
- CaO sensiblement égale ou supérieure à 0,5 et sensiblement égale ou inférieure à 3 ; CaO substantially equal to or greater than 0.5 and substantially equal to or less than 3;
- MgO sensiblement égale ou supérieure à 0,5 et sensiblement égale ou inférieure à 3 ; - MgO substantially equal to or greater than 0.5 and substantially equal to or less than 3;
- Na2Û sensiblement égale ou supérieure à 0,1 et sensiblement égale ou inférieure à 0,8 ; - Na2O substantially equal to or greater than 0.1 and substantially equal to or less than 0.8;
- K2O sensiblement égale ou supérieure à 0,5 et sensiblement égale ou inférieure à 2,5 ; et éventuellement du pentoxyde de phosphore et notamment un pourcentage massique de pentoxyde de phosphore sensiblement égal ou supérieur à 0,005 et sensiblement égal ou inférieur à 0,25. - K 2 O substantially equal to or greater than 0.5 and substantially equal to or less than 2.5; and optionally phosphorus pentoxide and especially a mass percentage of phosphorus pentoxide substantially equal to or greater than 0.005 and substantially equal to or less than 0.25.
16. Elément solide selon la revendication 15, caractérisé en ce qu'il présente une densité sensiblement égale ou supérieure à 1 ,7 et sensiblement égale ou inférieure à 2,3 t/m3. 16. A solid element according to claim 15, characterized in that it has a density substantially equal to or greater than 1, 7 and substantially equal to or less than 2.3 t / m 3 .
17. Elément solide selon l'une des revendications 15 et 16, caractérisé en ce qu'il présente une porosité ouverte sensiblement égale ou supérieure à 5% et sensiblement égale ou inférieure à 30%. 17. Solid element according to one of claims 15 and 16, characterized in that it has an open porosity substantially equal to or greater than 5% and substantially equal to or less than 30%.
18. Elément solide selon l'une quelconque des revendications 15 à 17, caractérisé en ce qu'il présente une phase vitreuse.
18. Solid element according to any one of claims 15 to 17, characterized in that it has a glassy phase.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1459465A FR3026738B1 (en) | 2014-10-03 | 2014-10-03 | PROCESS FOR MANUFACTURING A SOLID ELEMENT IN MATERIAL OF CERAMIC TYPE, SUITABLE FOR USE IN PARTICULAR FOR STORING THE HEAT-ASSOCIATED SOLID ELEMENT |
FRFR1459465 | 2014-10-03 |
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WO2022047137A1 (en) * | 2020-08-31 | 2022-03-03 | Seramic Materials Limited | Elaboration of ceramic tiles made of industrial solid wastes |
RU2787164C2 (en) * | 2018-03-01 | 2022-12-29 | ОуСиПи СА | Method for manufacture of ceramic material for accumulation of heat energy |
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WO2019166741A1 (en) * | 2018-03-01 | 2019-09-06 | Ocp Sa | Method for producing a ceramic material for thermal energy storage |
RU2787164C2 (en) * | 2018-03-01 | 2022-12-29 | ОуСиПи СА | Method for manufacture of ceramic material for accumulation of heat energy |
CN109336573A (en) * | 2018-10-26 | 2019-02-15 | 王占军 | A kind of sial gitter brick |
US11964914B2 (en) * | 2019-12-31 | 2024-04-23 | Seramic Materials Limited | Industrial solid waste based construction and technical ceramics |
WO2022047137A1 (en) * | 2020-08-31 | 2022-03-03 | Seramic Materials Limited | Elaboration of ceramic tiles made of industrial solid wastes |
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FR3026738B1 (en) | 2020-01-17 |
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