• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to an adjuvant for a cementitious or refractory concrete composition comprising, by weight, with respect to its total mass, at least: (a) from 20% to 70% of at least one organic aluminum acid, ( b) from 3% to 20% of at least one deflocculant selected from a carboxylic acid polymer, a carboxylic acid, a salt thereof, or a mixture thereof, and, (c) from 7% to 44% d at least one mineral oxide. The invention also relates to the use of such an adjuvant to improve the drying time of a refractory concrete composition or to improve the permeability of a refractory concrete composition. The invention finally relates to a cement composition and a refractory concrete composition each comprising such an adjuvant.
    公开号:FR3035399A1
    申请号:FR1553723
    申请日:2015-04-24
    公开日:2016-10-28
    发明作者:Jean Michel Auvray；Farida Kebli；Michaël Lievin；Kamel Benyahia；Christoph Wöhrmeyer
    申请人:Kerneos SA；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD TO WHICH THE INVENTION RELATES The present invention relates to the field of adjuvants for compositions based on hydraulic binders, such as cements or refractory concretes. In particular, the invention relates to an adjuvant for a cement composition or refractory concrete comprising a specific combination of an organic acid of aluminum, a deflocculant and a mineral oxide, in particular for improving the evacuation of water during the drying of refractory concrete. It also relates to a cement composition and a refractory concrete composition comprising this adjuvant. The invention also relates to the use of such an adjuvant to improve the drying time of a refractory concrete composition or to improve the permeability of a refractory concrete composition. BACKGROUND OF THE INVENTION Refractory concretes, in particular dense refractory concretes, are known for their exceptional property of resistance to high temperatures (ranging from 300 ° C. to 1800 ° C.) and are therefore used for this reason for coating furnaces iron and steel or other applications in high temperature. In fact, the furnaces must be able to withstand thermal, mechanical or chemical attacks. In general, a refractory concrete is manufactured by mixing, in a kneading device, a refractory aggregate (tabular alumina, corundum, bauxite, magnesia, alumina silicates, dolomite, etc.), an aluminous binder, optionally ultra-fine particles, such as silica fume or a powder of alumina, or even one or more adjuvants, such as a molding aid and mixing water. Once kneaded, we obtain a fresh concrete that is manageable and will be used to shape the desired structure. This is then consolidated by drying. During this drying, the refractory concrete develops a certain mechanical resistance (cure period). This consolidation phase then gives way to a dehydration phase of the refractory concrete. This leads to the elimination of free water and crystallization water. However, it has become apparent that the step of drying by increasing the temperature is problematic when producing refractory concretes and in particular dense refractory concretes. This density certainly improves the corrosion resistance of the refractory concretes, but it is problematic during the drying step since this density is accompanied by a low permeability which hinders the evacuation of the water, namely free water and crystallization water. Indeed, the amount of water that can be discharged by a material 10 forming a closed chamber is a function of the permeability of this material. It should not be confused with the amount of water that seeks to escape from a closed chamber material at a given temperature and pressure. In general, for economic reasons, the step of drying the refractory concretes must be as fast as possible. To do this, it is often necessary to heat them, for example at a temperature of around 300 ° C. However, when the amount of water that seeks to escape the refractory concrete is greater than the amount of water effectively discharged by this material, a risk of explosion appears. In fact, the free water and the crystallization water liberated lead to the formation of vapor. In the case of a rise in temperatures too fast during the drying step, the vapor pressure may exceed the mechanical strength of the concrete thus formed and lead to the explosion thereof. To date, to limit the risk of explosion during the drying step of the refractory concrete, a first solution is to set up cycles of heating said soft and slower refractory concretes. These heating cycles increase the duration of the drying and are not economically favorable. A second solution is to modify the permeability of the material, without greatly affecting its porosity so as not to risk weakening said material.
    [0002] The porosity is similar to the amount of void present inside a material and the permeability corresponds to the way its voids are arranged between them. Increasing the porosity often amounts to making a material less mechanically resistant, while increasing its permeability allows the water to be evacuated more easily during drying.
    [0003] One of the existing solutions for improving the permeability of the material is to use polymer fibers (polypropylene or polyvinyl). Nevertheless, this solution is effective only if the heating temperatures exceed the melting temperature of the fibers. This solution does not reduce the risk of explosion that occurs as soon as the temperature of the material exceeds 100 ° C. Moreover, it is difficult to disperse said fibers homogeneously in a mixture of dry concrete, that is to say in which the water has not yet been added. The heterogeneous material has areas at high risk of explosion. Finally, to preserve the flowability of a concrete comprising these fibers, it is necessary to add more water to the concrete formulation. However, an increase in the amount of water in the formulation of a refractory concrete results in an increase in the porosity of this refractory concrete after drying. As a result, such refractory concrete has a lower final quality. A third solution is to add metallic aluminum in the initial formulation of the refractory concrete. Indeed, the aluminum metal hydrolyses during the pH increase triggered by the hydration of said concrete. This hydrolysis reaction releases hydrogen which, bubbling through the material creates evacuation channels. These evacuation channels are used to evacuate the water during the drying of the refractory concrete. However, this solution has a significant risk of hydrogen explosion released during the installation of large parts in a confined environment. There is therefore a real need to develop new additives for cement compositions and / or for refractory concrete compositions which make it possible to limit the risks of explosion during rapid drying of refractory concretes while retaining at best the final properties. said refractory concrete formed, namely its compressive strength, robustness, etc., and this, while not affecting further its rheology. Indeed, it is desirable that the rheology of the refractory concrete thus formed, namely its workability (consistency) and workability, is not affected by the addition of a new adjuvant.
    [0004] The object of the present invention is thus to propose a new additive for a cementitious or refractory concrete composition, in particular dense refractory concrete, avoiding at least partly the aforementioned disadvantages.
    [0005] OBJECT OF THE INVENTION More particularly, according to the invention, an adjuvant is proposed, for example for a composition based on a hydraulic binder, such as a cementitious or refractory concrete composition, comprising, in mass with respect to its mass. At least: (a) from 20% to 70% of at least one organic acid of aluminum, (b) from 3% to 20% of at least one deflocculant selected from a carboxylic acid polymer, carboxylic acid, a salt thereof, or a mixture thereof, and (c) from 7% to 44% of at least one inorganic oxide. The present invention also relates to a cement composition comprising, by weight, with respect to the total mass of said cement composition, at least: from 20% to 70%, preferably from 30% to 60% and ideally from 40% to 60%; % of a hydraulic binder, and - from 30% to 80%, preferably from 40% to 70% and most preferably 60% of an adjuvant according to the invention, - optionally from 0% to 10% of other additives . Another subject of the invention relates to a refractory concrete composition comprising at least, by weight, with respect to the total mass of the refractory concrete composition, from 1% to 5%, preferably from 2% to 4% , and in particular from 2.5% to 3.5% of a cement composition as defined above, and from 95% to 99%, preferably from 96% to 98% and in particular of 96.5% 25 to 97.5% of a granular mixture composed of at least one granulate and fines. The present invention also relates to the use of an adjuvant as described above to improve the drying time of a refractory concrete composition or to improve the permeability of a refractory concrete composition.
    [0006] In the context of the present invention, the term "concrete" refers to a mixture of hydraulic binder, aggregates, water and optionally adjuvants and additions of other specific additives; a hydraulic binder means a material which, when tempered with water, hardens cold, without the addition of another reactant, and in both air and water, and is capable of agglomerating aggregates with one another; ; when the "hydraulic binder" is mixed with water, and hardens on contact, it is said to take hold; the term "cement" refers to a hydraulic binder in powder form obtained by grinding a clinker and possibly additives, the clinker being generally formed of hard calcium aluminate nodules; - "granulate" means a set of mineral grains of natural and / or artificial origin which has a dimension greater than or equal to 0.5 mm, such as sands, chippings, pebbles, gravel (meeting 10 in particular to the NFP 18-101 standard); - "fines" or "fillers" means a set of particles or mineral powders also of natural or artificial origin having a dimension less than 0.5 mm; the size of fines, of a sand, of aggregates or more generally of a constituent of a granular mixture, corresponds to its diameter if this constituent is of spherical shape; if the constituent is not a spherical shape, its dimension corresponds to the length of its primary axis, that is to say the longest straight line that can be drawn between an end of this component and an opposite end; The particle size of a powder corresponds to the size distribution of its particles. For the purposes of the invention, and unless otherwise specified, the indication of an interval of values "from X to Y" or "between X and Y" in the present invention, means to include X and Y values.
    [0007] According to the invention, all the percentages by weight, without specific indication to the contrary, are expressed with respect to the masses of dry matter of the compositions (binder, cement or even concrete). DETAILED DESCRIPTION OF AN EXEMPLARY EMBODIMENT The following description with reference to the accompanying drawings, given as non-limiting examples, will make it clear what the invention consists of and how it can be achieved. In the accompanying drawings: FIG. 1 represents the permeability in milli Darcy (mD) of two refractory concretes (Bi and B2) comprising an adjuvant according to the invention and two comparative refractory concretes (83 and B4); FIG. 2 shows the evolution of the internal pressure in bars as a function of the temperature in degrees Celsius (° C.) of the two refractory concretes according to the invention (B1 and B2) and of the two comparative refractory concretes (B3 and B4). ); FIG. 3 gives the percentage mass loss (/ 0) as a function of the temperature in degrees Celsius (° C) of the two refractory concretes according to the invention (B1 and B2) and of the two comparative refractory concretes (B3 and B4) Measured by thermogravimetric analysis (TGA); FIG. 4 represents the compression tension at break after drying, in Mega Pascal (MPa), of the two refractory concretes according to the invention (B1 and B2) and of the two comparative refractory concretes (B3 and B4), these four concretes. refractories having been dried according to two different drying methods (first method and second method); and FIG. 5 is a graph representing the applied load (AL / Lo) expressed as a percentage (%) as a function of the temperature in degrees Celsius (° C) of the two refractory concretes according to the invention (B1 and B2) and of the two comparative refractory concretes (B3 and B4).
    [0008] The Applicant has endeavored to develop a new admixture for a cement composition or refractory concrete, this refractory concrete having to be particularly dense and resistant to high temperatures (1300 ° C.) and corrosive atmospheres. The Applicant has shown that, unexpectedly, the combination of three particular components according to the invention adjuvanted to a cement composition made it possible to form a refractory concrete having a good compromise between, on the one hand, a better permeability facilitating the evacuation of the water during drying, and, secondly, a suitable porosity ensuring good mechanical strength.
    [0009] In addition, the particular combination of the components of the adjuvant according to the invention makes it possible to form a refractory concrete whose mechanical properties are suitable or even preserved (compressive strength, robustness, etc.), while limiting the risks of explosion when drying. Furthermore, and as will be demonstrated in the experimental section below, the combination of the components of the adjuvant according to the invention surprisingly has a synergistic activity which makes it possible to improve the permeability of refractory concrete with respect to to the combination of two of the components, while preserving in the fresh state (TO) a quite satisfactory consistency. For this purpose, the subject of the present invention is an adjuvant for a composition based on a hydraulic binder, such as a cementitious or refractory concrete composition, comprising, by weight, with respect to its total mass, at least: ) from 20% to 70% of at least one organic acid of aluminum, (b) from 3% to 20% of at least one deflocculant, and (c) from 7% to 44% of at least one oxide mineral. In particular, the adjuvant preferably comprises: (a) from 48% to 61% of said organic aluminum acid, (b) from 5% to 13% of said deflocculant, and (c) from 19% to 34% of said mineral oxide. Thus, the adjuvant (dry) according to the invention comprises three main components. The first component is (a) an organic aluminum acid selected from, for example: aluminum lactate, magnesium lactate, calcium lactate, zinc lactate, or a mixture thereof. Preferably, (a) the organic acid of aluminum is an aluminum lactate, also called aluminum tris (2-hydroxypropanoate). Generally, aluminum lactate has a lactic acid to alumina mass ratio of from 1.0 to 3.0, preferably from 1.2 to 1.6. In other words, the mass of all the lactic acid functions is 1.0 to 3.0, preferably 1.2 to 1.6 times greater than the mass of all the aluminum ions A13 + these ions. aluminum from alumina A1203 in aqueous solution.
    [0010] By way of example, an aluminum lactate suitable for the present invention has the CAS No. 18917-91-4 and can be marketed under the reference M160P by Taki Chemical Co., Ltd. Its molar ratio of lactic acid to A1203 alumina is 1.6. The product designated under the reference AI-lactate 512009001 or 512009002 sold by the company Dr. Lohmann 3035399 8 GmBH is also suitable for the present invention. Without being bound by any theory, the Applicant is of the opinion that the organic acid according to the invention makes it possible to improve the permeability of a refractory concrete composition in which it is integrated, because of its gelling power which occurs during the complexion of calcium from the cement, and / or magnesium may come from the inorganic oxide, when it is for example magnesia, or the aggregate used. As will be illustrated below, the effect of the organic acid according to the invention on the permeability will be increased by the combination with both a deflocculant and a mineral oxide.
    [0011] The second component is (b) a deflocculant. Advantageously, the deflocculant is chosen from: a carboxylic acid polymer, a carboxylic acid, a salt thereof, or a mixture thereof. In particular, the carboxylic acid polymer or a salt thereof is selected from: an acrylic acid polymer, a polyacrylic acid polymer, a methacrylic acid polymer, a salt thereof or a mixture thereof. By way of example, (b) the carboxylic acid polymer may be a sodium polyacrylate. In general, a sodium polyacrylate suitable for the present invention preferably has a degree of polymerization of between 2,000 and 10,000, preferably between 3,500 and 8,000.
    [0012] Preferably, (b) the carboxylic acid polymer has a weight average molecular weight of between 6000 and 8000. By polymerization degree is meant the number of monomer units contained in a macromolecule, that is, the number of monomer units contained in a polymer chain.
    [0013] In particular, when the deflocculant (b) comprises a carboxylic acid polymer, it represents, by weight, relative to the total weight of the deflocculant (b) from 0% to 20%, preferably from 3% to 15% and typically from 6% to 12%. In general, the carboxylic acid may be selected from: a citric acid or a salt thereof, such as an alkali metal salt, preferably (d) the carboxylic acid is a trisodium citrate. Preferably, when the deflocculant (b) comprises a carboxylic acid or a salt thereof, it represents, by weight, relative to the total weight of the deflocculant (b) from 0% to 20%, preferably 3% at 15% and typically from 6% to 8%. The deflocculant according to the invention provides a fluidifying effect to the refractory concrete composition in which it is integrated, insofar as it is able to separate the constituents of the granulate and / or to prevent them from sticking together. to others. In addition, the deflocculant forms a complex with calcium derived from aluminous cement generally included in refractory concrete. The formed complex makes the hydraulic setting slower. Thus, advantageously, the refractory concrete can be worked and shaped over a relatively long time before hardening. Also, thanks to the deflocculant, the final refractory concrete composition comprises a smaller amount of water. Also, when the deflocculant (b) is a carboxylic acid and / or a carboxylic acid polymer, or a salt thereof, such as sodium polyacrylate and / or trisodium citrate, it has been found that this allows advantageously to improve the rheology of the refractory concrete, in particular giving it a good fluidity. In addition, the carboxylic acid or one of its salts makes it possible to use less water in the final composition of the refractory concrete. In particular, sodium citrate mixed with organic aluminum acid, or even a carboxylic acid polymer and mineral oxide, improves the consistency of the concrete by making it less firm. The third component of the adjuvant according to the invention is (c) a mineral oxide or a salt thereof, such as a calcium salt or a magnesium salt. Preferably, (c) the inorganic oxide is a metal oxide selected from: a magnesium oxide, or a mineral species formed of calcium and magnesium carbonate, such as dolomite of the formula CaMg (CO 3) 2. Advantageously, the inorganic oxide (c) is magnesium oxide and / or dolomite. For example, said preferred inorganic oxide used in the composition of the adjuvant according to the invention can be taken in the form of a magnesium oxide powder comprising at least 90% by weight of magnesia, and preferably at least 95% by weight. % of magnesia. This magnesia preferably has a BET specific surface area of between 0.5 square meters per gram (m 2 / g) and 3 m 2 / g, or more specifically of the order of 1 m 2 / g.
    [0014] By "BET surface area" is meant the actual area of a porous solid, as opposed to its apparent surface area. It is a surface per unit mass, also called total mass area of said porous solid. Here, it is defined according to the method Brunauer, Emmett and Teller (BET), described by the standard ISO 5 9277: 1995. As will be demonstrated in the examples below, the combination of compounds (a) to (c) of the adjuvant according to the invention makes it possible, via a synergistic action, to improve the permeability of refractory concretes. The percentage by weight of each of the components included in the adjuvant according to the invention is adjusted empirically so as to obtain an acceptable compromise on the use characteristics of the refractory concrete, that is to say, for example, its mechanical characteristics, its resistance to high temperatures, its permeability or its workability. By thus adjusting the weight percentage of each of the components in the additive, the use characteristics of the refractory concrete are close to those of the known refractory concretes, but the permeability is higher, which facilitates the drying of said refractory concrete according to the invention. 'invention. Thus, the adjuvant according to the invention, by improving the permeability of the refractory concrete in which it is incorporated, facilitates the evacuation of the water during its drying, which at least partly limits the risk of explosion of the concrete. refractory when fast drying. Moreover, the adjuvant according to the invention makes it possible to retain most of the mechanical strength properties of refractory concretes. Thanks to the adjuvant according to the invention, the refractory concrete has good characteristics of use, such as workability and maneuverability. It is indeed not necessary to add water beyond what is necessary to improve the rheology of the concrete formed with the adjuvant. This addition of additional water would increase the porosity of the concrete and could thus affect its mechanical properties.
    [0015] Also, thanks to the preferred adjuvant according to the invention, the shaping and pourability of the refractory concrete are easier. As mentioned above, the adjuvant according to the invention is particularly suitable for formulations of cement-based refractory concretes, such as aluminous cement.
    [0016] The present invention also relates to a cement composition (in the dry state) comprising, by weight, with respect to the total mass of said cement composition, at least: from 20% to 70%, preferably from 30% to 70% by weight, % to 60% and ideally 40% of a hydraulic binder, and from 30% to 80%, preferably from 40% to 70% and most preferably 60% of an adjuvant according to the invention as described above. - optionally from 0% to 10%, preferably from 0.2% to 5% of other cementitious additives (which will be described below).
    [0017] In particular, the hydraulic binder comprises, by weight, with respect to its total mass at least 65%, preferably from 70% to 99%, typically from 80% to 95% of a calcium aluminate. Within the meaning of the invention, at least 65% by weight of calcium aluminate includes the following values in percentages: 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, or 99.9. In general, said calcium aluminate contains traces of mineral oxides, namely less than 5% by weight relative to its total mass, of traces of mineral oxides. These oxides are, for example, SiO 2, Fe 2 O 3, TiO 2, K 2 O, Na 2 O, etc. Generally, the hydraulic binder suitable for the invention comprises the following mineralogical phases (cementitious abbreviation C = Ca0 and A = Al2O3): CA, CA2, A, C12A7 or a mixture thereof. By way of example, it may comprise the following chemical composition expressed in mass with respect to the total mass of said hydraulic binder: from 40% to 85% of Al 2 O 3; from 15% to 40% of Ca 2 0.2% to 8% SiO 2; from 0.1% to 10% Fe 2 O 3; Traces of other mineral oxides. The commercial products marketed by KERNEOS under the trade names Secar®71 or Secar080, Secar®51 or CMA72 are suitable as hydraulic binders for the invention. The cement composition according to the invention is obtained by mixing the various compounds in a dry state. Indeed, the cement composition is prepared according to the following step: the adjuvant according to the invention is mixed with the hydraulic binder as defined above and optionally with cement additives for 10 seconds to 10 minutes, in 2 to 5 minutes in a mixer, such as a kneader having a speed of rotation ranging from 120 to 230 rpm, in particular from 130 to 190 rpm. At the outlet, an adjuvant cement is obtained, that is to say a powder forming a new hydraulic binder.
    [0018] This cement composition makes it possible in particular to manufacture a refractory concrete composition, such as a dense refractory concrete composition. Thus, the present invention also relates to a refractory concrete composition comprising at least, by weight relative to the total mass of the refractory concrete composition in the dry state, ie not spoiled with water, - 1% at 5%, preferably from 2% to 4% and in particular from 2.5% to 3.5% of a cement composition as defined above, and from 95% to 99%, preferably of 96% at 98% and in particular from 96.5% to 97.5% of a granular mixture composed of at least one granulate and fines, from 0% to 10% of concrete additives. Preferably, the granular mixture comprises, by weight, relative to its total mass, from 70% to 95% of the granulate and from 5% to 30% of fines. Thus, in general, per 100 parts by weight of a mixture comprising a cementitious composition and a granulate as defined above, the refractory concrete according to the invention comprises: (a) from 0.34 to 2 parts by weight preferably 0.7 to 1.5, typically 0.81 to 1.03 parts by weight, and most preferably 1 part by weight of said at least one organic aluminum acid, such as aluminum lactate; (b) from 0.08 to 0.34 parts by weight, preferably from 0.10 to 0.34, such as 0.2 parts by weight of at least one deflocculant, such as sodium polyacrylate and / or trisodium citrate; (c) from 0.11 to 0.74 parts by weight, preferably from 0.32 to 0.54 parts by weight, such as 0.5 parts by weight of said at least one inorganic oxide, such as magnesia.
    [0019] By way of example, the granulate according to the invention may be composed of refractory aggregates or insulating aggregates, namely resistant to high temperatures, ranging for example from 300 ° C. to 1800 ° C., generally up to 300.degree. 1300 ° C or at least 1000 ° C.
    [0020] Generally, the raw materials of the refractory aggregates are unstable at cooking, which is why they are advantageously stabilized by a "chamotte" precooking which also, in general, makes it possible to reduce the porosity of the aggregate to the level of longed for. Thus, the granulate according to the invention is preferably chosen from an aggregate obtained by calcination. Such an aggregate obtained by calcination suitable for the present invention may be chosen from: a dolomite, a magnesia (compound independent of magnesium oxide that may be present in the adjuvant as inorganic oxide), alumina silicates , tabular alumina, calcined bauxites, or fused alumina, synthetic mullite, synthetic spinels or a mixture thereof. For example, dolomite is made from a double carbonate of lime and magnesia calcined at high temperature (1800/1900 ° C) to obtain porosities less than 5% and stabilize the dolomite. The magnesia aggregate can be obtained by two distinct routes: either by high-temperature calcination of giobertite or by precipitation and then calcination of magnesium salts in seawater. Synthetic mullites can be obtained by melting. bauxite and silica or alumina and silica or they can be obtained by sintering a mixture of clay, kaolin and alumina. These aggregates obtained by calcination are conventional and known to those skilled in the art.
    [0021] However, certain types of granulate suitable for the present invention and having high resistance at high temperature are not obtained by calcination. These types of granules correspond in particular to alumina silicates. By way of example, andalusite (or kerphalite), which is an alumina silicate present in metamorphic rocks in the form of white crystals, is suitable as a granulate in the context of the present invention. In general, the granules have a particle size of less than 30 millimeters (mm), preferably have a particle size distribution ranging from 0 to 10 millimeters (mm). For example, the following granular fractions are suitable: 0 / 0.5 mm, 0.25 / 8 mm, 0.5 / 1 mm, 3/6 mm, 6/14 mm, 14/28mesh (ie 3035399 about 1, 4 / 0.84 mm), 28/48 mesh (ie about 0.6 / 0.3 mm), less than 48 mesh (or about less than 0.3 mm). The choice between these aggregates is made among other things depending on the thickness of the work to achieve. The refractory concrete or cement composition according to the invention may comprise other additives, other than the adjuvant according to the invention as defined above. These other additives can be air entraining agents, incorporated in a small proportion to modify, improve or supplement some of the characteristics of finished and dry concrete.
    [0022] For example, additives acting on setting and hardening time, such as accelerators which shorten the time between the hydration of the binders and their setting, and retarders which lengthen the time between the hydration of the particles. of a binder and the beginning of its taking. As accelerators, mention may be made, for example, of lithium salts such as carbonate, calcium or sodium chlorides, certain alkalis (sodium hydroxide, potassium hydroxide, ammonia) or their salts (potassium or sodium sulphate). Examples of retardants are carbohydrates (sugars, glucose, starch, cellulose), various acids or salts of acids, or alkaline phosphates (such as sodium tripolyphosphate).
    [0023] Additives acting on plasticity and compactness, such as plasticizers and fluidifiers, known as water reducers, may also be mentioned. As a plasticizer, for example, bentonite, fatty lime, ground limestone, fly ash and kieselguhr may be incorporated. As the plasticizer, it is possible to use polyacrylates, polycarboxylates, alkaline phosphates, lignosulphates, resin soaps or synthetic detergents. The dry composition of refractory concrete is prepared according to a conventional method known to those skilled in the art, namely by mixing the various constituents of the concrete, namely the cement composition defined above (and therefore comprising the adjuvant according to the invention. invention) with the granulate and optionally additives other than the adjuvant according to the invention in a mixer provided for this purpose. This dry concrete composition is then mixed with water in order to obtain a fresh concrete composition which comprises in particular the following successive stages: - the dry refractory concrete composition is introduced into a mixer, such as a kneader; As defined above, mixing water is added to the dry concrete composition and mixed / kneaded for 2 to 10 minutes at a rotation speed of 130 to 150 rpm, preferably 140 rpm. . Here, the water mixing rate, ie the amount of water relative to the weight of the dry concrete composition, is generally from 2% to 10%, preferably from 3% to 8%, ideally 5% at 8%. For the purposes of the invention, the mixing water also comprises the quantity of water possibly present in the various aggregates. Once the concrete composition is mixed with water, a concrete paste is obtained that can be sprayed or cast to produce a structure or a construction element that will be particularly resistant to very high temperatures. In particular, the refractory concrete may be used in the industrial sector of internal lining of ovens, blast furnaces, boilers, flues, chimneys, incinerators, etc. Finally, the present invention also relates to the use of the adjuvant according to the invention for improving the drying time of a refractory concrete composition and / or for improving the permeability of a refractory concrete composition. The present invention is further illustrated by the following examples. Unless otherwise specified, percentages are by mass. EXAMPLES 25 A) Test procedure The following test procedures were used to evaluate the characteristics of the various compositions tested: 1. Air permeability test (FIG. 1) The air permeability measurement is based on on the evaluation of the ability of a porous material to be passed through, through its pores, by gases or other fluids. The air permeability is expressed in milli Darcy (mD), a darcy equivalent to the permeability of a continuous and isotropic body through which flows a fluid of viscosity close to that of water at 20 ° C. at a rate of 16 centimeters per second (cm / sec) when subjected to a pressure of 1 atmosphere (atm). In order to determine the permeability of the refractory concretes of the examples below, ambient temperature of 20 ° C +/- 2 ° C is used at 70% +/- 10% humidity. The concrete sample is prepared and then placed in a disk-shaped Teflon® mold 100 mm in diameter and 25 mm thick on a Sinex vibrating table at a frequency of 50 Hz and having an amplitude of 0. , 3 mm according to the following protocol (3 vibrations: - the mold is filled to 50%, vibrated 30 s; - the mold is filled to 100%, vibrated 30 s; - vibrate 30 s additional. The sample is then cured in a humid chamber (20 ° C, 95% residual humidity) for about 24 hours, then it is demolded and steamed at 110 ° C +/- 2 ° C for at least 24 hours. hours.
    [0024] Once cooled, the thickness and diameter to the thousandth of an inch (which is equivalent to 2.54 cm) are measured and the sample is placed in a VacuPerm0 permeabilimeter based on the vacuum drop technique (the pressure in start of cycle is less than 0.1 atm to allow the acquisition of vacuum, when it reaches 0.75 atm, the permeability measurement stops). A software displays the result as well as the standard deviation which must remain less than 10% of the result. 2. Measurement of the In Situ Pressure of Water Vapor During Heating (FIG. 2) This test consists in placing the sample to be analyzed having a size of 300 × 300 × 100 mm under a radiant heater (5000 W) in order to obtain, at the end 3 minutes, a temperature of 600 ° C. The side faces of the sample are then thermally insulated with porous ceramic bricks. The sample is further equipped during molding with temperature and pressure gauges in the form of sintered metal round plates (012 x 1 mm) which are housed in the thickness of the sample to be analyzed. Each plate is welded to a metal tube having an internal diameter of 2.6 mm which starts from the cold face of the sample (opposite side to that surrounding the radiant heater) towards a pressure sensor. For temperature measurements, some 3035399 17 thermocouples (01.5mm) are inserted into the metal tube. In particular, a first gauge is placed at 2 mm distance from the heated face (temperature measurement), then five other pressure and temperature gauges are successively arranged at 10, 20, 40, 60 and 80 mm from the heated face. within a square of 10x10 cm2. The loss of mass during heating can be recorded via a scale on which the sample is placed. In situ pressure of water vapor is a function of temperature. Thus, the maximum pressure will be reached just before the end of drying, ie when the temperature is highest. 3. Thermogravimetric Analysis (TGA) Measurement (FIG. 3) ATG is a thermal analysis technique that consists of measuring the mass change of a sample as a function of time, for a temperature or a profile. given temperature (here, when drying the concrete sample to be analyzed).
    [0025] The procedure for carrying out this test consists in preparing and vibrating a sample of fresh concrete in a cube-shaped metal mold measuring 10 × 10 × 10 cm. A first temperature sensor is placed in the sample 1 cm from the edge and a thermocouple cable is placed in the center about 5 cm deep to measure the internal temperature of the sample. After placement, the sample is cured at 20 ° C at 100% residual moisture for 24 hours. The sample is then removed from the mold, placed in an oven and suspended by a platform attached to a scale. The follow-up as a function of the mass loss and the internal temperature of the sample is done by a temperature rise of the oven from 5 ° C./min to 600 ° C. with a 2 hour hold at this temperature. . With these analyzes, it is possible to identify the temperature ranges over which the water is removed from the refractory concretes, these temperature ranges corresponding to the ranges on which the mass of said refractory concretes drops. 4. Compressive strength test (standard NF EN 12390-4) (FIG. 4) The principle of the test is to subject a cylindrical test piece to a constant and increasing force until it breaks in order to determine its 3035399 18 compressive strength. The procedure for performing this test consists in preparing and vibrating a sample of fresh concrete in a 160x30x30mm stainless mold.
    [0026] After placement, the sample is cured at 20 ° C at 100% residual moisture for 24 hours. Optionally, the sample may be further heated at 110 ° C +/- 2 ° C for at least 24 hours following the curing step at 20 ° C. After the demolding of the sample to be analyzed, the mechanical performance measurements are made at the desired time on at least two bending bonuses, leading to compressions on 4 minimum half-prisms (lbertest press). Compression measures between 0 and 200 kN and bending is between 0 and 10 kN. 5. Refractory Character under Load (FIG. 5) according to IS01893 / EN993-8 This test makes it possible to observe the behavior of refractory concrete samples under temperature conditions of up to 1650 ° C. For this test, the sample is in the form of a specimen (0ext = 50mm, H = 50mm) with a hole in its center (0trou = 5 mm).
    [0027] The apparatus comprises an oven equipped with a control system, thermocouples for controlling the temperature and a device for placing the test piece under axial load and measuring its variation in height. An acquisition system records all the data of the device.
    [0028] B) Characterization of refractory concrete compositions according to the invention 1. Compositions tested a) Examples of adiuvant compositions Various adjuvant compositions according to the invention were prepared.
    [0029] The process for the preparation of these builder compositions comprises the following step: aluminum lactate C9H15A109 (Cas-No 1891791-4) is mixed with a sodium polyacrylate having a weight average molecular weight (Mw) of between 6000 and 8000 and magnesia MgO and / or citric acid for a period of 4 minutes at room temperature in a mixer L20 M20, the speed of the drive shaft being set at 190 rpm and the speed of the sweeper being set at 1500 rpm. The compositions of the adjuvants Ex.1, Ex.2 and Ex.3 according to the invention are illustrated in Table 1 below: Composition Ex.1 (%) Ex.2 (/ o) Ex.3 (%) Lactate of aluminum 58.82 57.1 62.50 Sodium polyacrylate 11.76 11.4 - Magnesia 29.42 28.6 31.25 Trisodium citrate - 2.9 6.25 5 Table I b) Examples of compositions of Cements From the composition of the adjuvant Ex.1 according to the invention, a cement composition according to the invention (FI) was manufactured. For comparison, two cement compositions according to the prior art (F2, F3) were also prepared according to the same procedure, except that the comparative cement composition F2 comprises a known fluidifying agent, Peramin A12000 based on polycarboxylate ether which is marketed by KERNEOS, and that composition F3 comprises sodium tripolyphasphoate (Na-TPP) with a molar mass of 368 g / mol.
    [0030] For this test, the cement compositions were prepared by mixing the product Secar71® (the chemical composition of which comprises from 67.5% to 70.5% Al 2 O 3, from 28.5% to 31.5% by weight). of CaO, traces of SiO2 and Fe2O3) with the adjuvant in the mixer Li5dige M20; the speed of the motor shaft being set at 190 rpm and the speed of the rambler being set at 1500 rpm.
    [0031] The cement compositions F1, F2 and F3 tested have the following formulations (Table 2): Formulation F1 (%) F2 (%) F3 (%) Hydraulic binder Secar7l® 50 96.67 99 Ex.1 50 Na-TPP adjuvant Table 2 c) Examples of concrete compositions Two refractory concrete compositions according to the invention B1 and B2 were A1200 3.33 3035399 prepared in a Perrier mixer from the cement composition according to the invention F1 above. one with a low cement content (B1) and the other with a medium cement content (B2). Two comparative compositions of low cementitious B4 refractory concrete and medium cementitious B4 were also prepared, respectively, from the comparative cement compositions F2 and F3 described above. The concrete compositions B1, B2, B3 and B4 tested are shown in Table 3 below (formulations F1 to F3 are those of Table 2). Low cement content Medium content (LCC) (° / 0) cement (MCC) (%) Compositions B1 B3 B2 B4 Tabular alumina 70 70 80 80 Spinel 15 15 5 5 1 9 9 5 5 Reactive alumina Binder: Secar 71® 3 3 7 7 F1 3 3 F2 3 F3 3 Water tempering rate (%) 5.2 5.3 Table 3 Refractory concrete B1 to B4 were prepared following the following procedure (CEN 196.1 and EN 1402 -4): - the raw materials (cement compositions F1, F2, and F3, aggregate, etc.) and water are first conditioned at least 24 hours at the set temperature of 20 ° C +/- 2 ° C (the formulations F1, F2 and F3 are in particular preserved in a dry and sealed container); the quantity of water necessary for the mixing is determined and weighed; the Perrier mixer (5L tank) is set at a slow speed of 140 ± 15 rpm for rotation and 62 ± 16 rpm for planetary movement; 2 kg of the cement formulations to be studied are introduced into a bowl whose walls are dry; - the mixing water is introduced in its entirety in 5 s maximum; 3035399 21 - kneaded for 2 min, - in 30 s, the walls of the bowl are scraped to remove the dry matter; - It kneads again 2 min. The refractory concretes according to the invention and according to the prior art are then dried according to either a first drying method or a second drying method, depending on the tests carried out. The first method of drying is to leave the concrete at room temperature, that is, 20 degrees Celsius (° C) for 24 hours. The second method of drying is to add an additional heating step with respect to the first method, namely heating the concrete to 110 ° C for 24 hours. As mentioned above in paragraph (A), the samples will be dried according to Method 1 or Method 2 depending on the tests carried out. For example, for the compressive strength test (Fig. 4) two sets of concretes B1 to B4 were prepared: one set with the first drying method and one set with the second drying method. 2. Results (FIGS. 1 to 5) a) Permeability (FIG. 1) FIG. 1 compares the permeability of the refractory concretes B120 and B2 according to the invention with those of the comparative refractory concretes B3 and 64. As shown in FIG. Well in Figure 1, concretes B1 and 62 comprising the adjuvant according to the invention (Ex.1) have a better permeability. Thus, the adjuvant according to the invention (Ex. 1) clearly improves the permeability of the refractory concretes studied.
    [0032] Indeed, the refractory concrete B1 according to the invention, that is to say the refractory concrete with a low cement content F1 comprising the adjuvant Ex.1 according to the invention, has a permeability nearly 300 times greater. Comparative refractory concrete 83 of similar composition. Likewise, the refractory concrete B2 according to the invention, namely the refractory concrete with a medium cement content F1 comprising the excipient Ex.1 according to the invention, has a permeability more than 1000 times greater than the comparative refractory concrete. B4 of similar composition. These results are confirmed by measurements of internal pressure at different points of the above-mentioned refractory concretes B1, B2, B3 and 64, during a temperature rise. The test includes measuring, using suitable sensors, the water vapor pressure and the temperature at different points of the refractory concrete samples B1 to B4 during a unidirectional heating of said samples. B) In-situ pressure of water vapor as a function of temperature (FIG. 2) FIG. 2 presents the results of this pressure measurement test for refractory concretes B1 and B2 according to the invention, and for refractory concretes In particular, it will be noted in this FIG. 2 that the internal pressure of the refractory concretes B1 and B2 adjuvanted with the adjuvant according to the invention (Ex.1) does not exceed 1 bar, whereas the pressure internal refractory concrete comparative B3 and B4 reaches 5 bar, or even more than 19 bar. These results prove that the water is more easily evacuated from the refractory concretes B1 and B2 according to the invention, which confirms that the permeability of said refractory concretes B1 and B2 according to the invention is improved compared with that of the comparative refractory concrete B3 and B4 of the prior art. Thus, this test shows that the adjuvant according to the invention is capable of greatly limiting the risk of explosion of refractory concretes according to the invention during their drying. C) Weight loss as a function of temperature (ATG measurement) (FIG. 3) As demonstrated above, the permeability is improved. Accordingly, the drying of refractory concretes according to the invention is also. In FIG. 3, it will be noted that the temperature range over which the water contained in the two refractory concretes B1 and B2 according to the invention is eliminated extends between about 100 ° C. and 150 ° C. This temperature range is narrower and ends at temperatures lower than the temperature range over which the water contained in the comparative refractory concrete B3 and B4, which extends between 100 ° C and 100 ° C, is eliminated. About 350 ° C. Thus, thanks to the adjuvant Ex.1 according to the invention, the drying of the refractory concretes B1 and B2 according to the invention is clearly improved since it becomes unnecessary to increase the temperature to complete said drying. These results go together with those obtained by the pressure test (FIG. 2). In fact, on the curves of FIG. 2, the maximum internal pressures reached in the materials are reached, these maximum internal pressures being reached just before the end of drying (the pressure of water vapor being a function of the temperature). ). Thus, the internal pressure of the refractory concretes B1 and B2 according to the invention is maximum for a temperature of about 105 ° C., whereas for the comparative refractory concrete B3, the internal pressure is maximum around 160 ° C., and that for comparative refractory concrete B4, the internal pressure is maximum around 220 ° C. d) Resistance in compression (FIG. 4) In order to verify that the improvement in the permeability does not deteriorate the mechanical properties, and in particular the mechanical strength, of the refractory concretes B1 and B2 according to the invention, the compressive strength was compared refractory concretes B1 and B2 according to the invention to that of comparative refractory concrete B3 and B4 of the prior art. As shown in FIG. 4, the refractory concrete B1 according to the invention has a compressive strength similar to that of the comparative refractory concrete B3, especially when these concretes have been dried according to the second drying method. B2 refractory concrete according to the invention sees its mechanical strength in compression fall by half compared to that of the comparative refractory concrete B4. However, the mechanical compressive strength of refractory concrete B2 according to the invention remains quite satisfactory, and it is of the same order of magnitude as that of refractory concrete B1 according to the invention and comparative refractory concrete B3. e) Refractory Character under Load (FIG. 5) The refractoriness under load of the refractory concretes B1 and B2 according to the invention was also compared with that of the comparative refractory concretes B3 and B4. For this purpose, it was realized on the refractory concrete B1 to B4 an experiment to evaluate their refractoriness under load. The results of this comparison appear in FIG. 5. Thus, it can be seen that the refractory behavior under load of the refractory concretes B1 and B2 according to the invention is quite similar to that of the comparative refractory concretes B3 and B4 of the art. prior. f) Conclusion 3035399 24 Thus, the refractory concretes B1 and B2 comprising the excipient Ex.1 according to the invention have a better permeability than the comparative refractory concretes B3 and B4 of the prior art. In addition, the refractory concretes B1 and B2 comprising the adjuvant Ex.1 according to the invention have mechanical strength properties at least in part similar to those of comparative refractory concretes B3 and B4 of the prior art. Therefore, the adjuvant Ex.1 according to the invention contributes to the improvement of the drying of the refractory concretes according to the invention, in particular by reducing the risk of explosion during their drying, without deteriorating the refractory qualities. said refractory concretes according to the invention. C) Characterization of the Adjuvant and Cement Compositions According to the Invention The purpose of the following test is to demonstrate the synergistic activity of the constituents of the adjuvant according to the invention when taken in combination. 1. MCC Concrete Test Compositions For this test, various additive formulations were tested to make refractory concrete. The "base composition" of the refractory concretes tested, namely the mixture of cement and granulate, is given in Table 4; while the final compositions of the concretes tested (hereinafter B5 to B11) are presented in Table 5. The adjuvant, cement and concrete compositions were prepared from the same raw materials and according to the same procedure. than the one described in test (B) above according to the first method ("air 24h") or the second method ("110 ° C 24 hours") of drying. Constituents Base MCC Concrete (io) Table Alumina 1 / e-8 mm 35.0 Table Alumina 6-14 mesh (ie 3.4 to 1.4 mm) 15.0 Table Alumina 14-28 mesh (ie 1.4 to 0.6 mm) 8.0 Tabular alumina 28-48 mesh (ie 0.6 to 0.3 mm) 9.0 Tabular alumina <48 mesh (ie <0.3 mm) 7.0 Tabular alumina -325 mesh (ie - 0.044 mm) 6.0 Reactive Alumina 5.0 3035399 25 Constituents Base MCC Concrete (%) Smoke Silica 5.0 Secar 71® 10.0 Total 100 Table 4 For 100 parts by weight of base concrete according to base composition given in Table 4 above. different additive compositions were studied (Table 5): Tested concretes B5 B6 B7 B8 - B9 BBBBBB 10 11 12 13 14 15 Lactate 0 1.0 0 1 1 1 1 1 1 1 of Al Poly- 0 0 0.2 0 0.2 0.2 0.2 0.2 0 sodium acrylate Citrate 0 0 0 0 0 0 0 0 0.1 0.1 0.05 trisodium Magnesia 0 0 0 0.5 0 0 0.5 0.5 0 Tripoly- 0.0 0 0 0.03 0 0.03 0 0.03 0 sodium phosphate 3 * RESULTS 0.0 0.2 0.3 0.59 1.0 1.21 0.48 Permeability 5 0 2 9 (mD) to 110 ° C 0.73 1.30 1 1.3 1.48 Consistency (initial 11 »210 220 230 215 205 195 190 195 225 215 180 Mechanical resistance (MPa) c In the air 24h 9.1 8.8 - 8.8 7.8 7.9 8.7 8.2 - - - 0 I 110 ° C 18, 14, - 8.1 9.2 10.0 7.7 6.9 - - - 0 5 Compres A air 24h 90, 64, - 62.1 52, 53.5 59.9 57.3 - - - 0 20 - - 97, 110 ° C 165 155 - 100, 115, 92.0 84.6 5 * Molar mass = 368 g / mol Table 5 The water mixing rate for all the B5 to B15 concretes tested is 5.50%. Table 5 shows that the concrete comprising the adjuvant according to the invention has a better permeability, while having a rheology (fresh flow determined at the Abrams cone) quite satisfactory. Indeed, the permeability of a reference concrete B5 containing no adjuvant other than a setting retarder (sodium tripolyphosphate) has a permeability of 0.05 mD for a consistency of 210 mm. For a substantially identical consistency, the concretes prepared with the adjuvant according to the invention has a permeability multiplied by a factor of 26 (for example between the concretes B11 or B14 according to the invention and the reference concrete B5), or even of a factor 30 between the concrete B15 according to the invention and the reference concrete B5.
    [0033] This table also shows that the concrete comprising only aluminum lactate alone (B6 concrete) has a low permeability of 0.20 mD. When magnesia (concrete B10) is added, the permeability reaches 0.59 mD, which is an increase in permeability by a factor of 3. And when sodium polyacrylate (concrete B11) is added, permeability is reached. 1.3 mD, an increase in permeability by a factor of 6.5 relative to concrete B6. Also, the permeability of a concrete comprising the adjuvant according to the invention based on trisodium citrate is greatly increased relative to the reference concrete or with respect to concrete compositions comprising only one or two of the essential compounds of the invention. adjuvant according to the invention, such as compositions B6 to B10 and B13, while having an acceptable rheology. For example, the permeability is increased by a factor of 6 between the concrete B14 according to the invention and the concrete B6 comprising only aluminum lactate, or a factor 2.7 between the same concrete B14 according to the invention. invention and concrete B13 (aluminum lactate + trisodium citrate), a variation of + 171%.
    [0034] Therefore, the combination of the three components of the admixture significantly improves the permeability of a refractory concrete in which they are incorporated with respect to the use of only one or two of these components. In addition, it can be seen from Table 5 that the use of a retarder (sodium tripolyphosphate) in the admixture very slightly lowers the permeability of the concrete (B12). 2. Test compositions of LCC concrete For this test, various additive formulations were tested in order to manufacture refractory concretes. The "base composition" of the concretes tested, namely the mixture of cement and granulate, is given in Table 6; while the final compositions of the concretes tested (hereinafter referred to as B16 to B18) are presented in Table 7. Also for this test, the adjuvant, cement and concrete compositions were prepared from the same raw materials and according to the same procedure as that described in test B) above according to the second drying method. Constituents Base LCC Concrete (io) Table Alumina 3-6 mm 33 Table Alumina 8-14 mesh (ie 2.38 to 1.4 mm) 16 Table Alumina 28-48 mesh (ie 0.6 to 0.3 mm) ) 6 Table Alumina <48 mesh (ie <0.3 mm) 5 Frosted Spinel 0.5-1.0mm 9 Spinel frit 0-0.5mm 4 Sintered Spinel 0-0.09 mm 10 Reactive Alumina 11 Secar 71® 6 Total 100 Table 6 For 100 parts by weight of base concrete according to the base composition given in Table 6 above, various additive compositions were studied (Table 7): Additive Constituents according to Other Perme Consistency the invention (%) additives ability (mm) (%) (mD) Tested concretes Lactate Sodium polyacrylate Magnesia Peramin aluminum A1200 B16 - - - 0,02 0,02 200 B17 1,00 0,20 _ - 0 , 75 195 B18 1.00 0.20 0.50 190 Table 7 The water mixing rate for all the B16 to B18 concretes tested is 5.00%. Like the previous test shown in Table 5, Table 7 shows that the permeability is better when the concrete comprises the adjuvant 3035399 28 according to the invention B18. Indeed, a very low permeability is obtained when the concrete B16 is additive of a deflocculant according to the prior art, namely here the Peramin A1200®. This value is improved when two components of the adjuvant according to the invention are added and even more so when all three, namely aluminum lactate, sodium polyacrylate and magnesia, are added. Indeed, there is an increase in the permeability of more than 47% between concretes B17 and B18. Thus, it is indeed the combination of these constituents which makes it possible to increase the permeability of the refractory concretes, while not affecting their mechanical strength and their robustness, as has been demonstrated in the test B) ci -above. Although the invention has been described in connection with a particular embodiment, it is obvious that it is in no way limited thereto and that it comprises all the technical equivalents of the means described and their combinations if they These are within the scope of the invention.
    权利要求:
    Claims (13)
    [0001]
    REVENDICATIONS1. An adjuvant for a hydraulic binder composition, such as a cementitious or refractory concrete composition, comprising, by weight, based on its total mass, at least: (a) from 20% to 70% of at least an organic acid of aluminum, (b) from 3% to 20% of at least one deflocculant selected from a carboxylic acid polymer, a carboxylic acid, a salt thereof, or a mixture thereof, and c) from 7% to 44% of at least one mineral oxide.
    [0002]
    An adjuvant according to claim 1 comprising (a) from 48% to 61% of said organic aluminum acid, (b) from 5% to 13% of said deflocculant, and (c) from 19% to 34% of said inorganic oxide . 15
    [0003]
    3. Adjuvant according to one of claims 1 and 2, wherein (a) the organic acid of aluminum is selected from: aluminum lactate, magnesium lactate, calcium lactate, zinc lactate, or one of their mixtures, preferably (a) the organic acid of aluminum is an aluminum lactate.
    [0004]
    The adjuvant of claim 3, wherein (a) the aluminum lactate has a mass ratio of lactic acid to alumina ranging from 1.0 to 3.0, preferably from 1.2 to 1.6.
    [0005]
    5. Adjuvant according to one of claims 1 to 4, wherein the carboxylic acid polymer or a salt thereof is selected from: an acrylic acid polymer, a polyacrylic acid polymer, a methacrylic acid polymer , A salt thereof, such as sodium polyacrylate, or a mixture thereof, preferably (b) the carboxylic acid polymer is a sodium polyacrylate.
    [0006]
    The adjuvant of claim 5, wherein (b) the sodium polyacrylate has a degree of polymerization of from 2,000 to 10,000, preferably from 3,500 to 8,000.
    [0007]
    7. Adjuvant according to one of claims 1 to 4, wherein the carboxylic acid or a salt thereof is selected from: a citric acid or a salt thereof, such as an alkali metal salt, preferably ) the carboxylic acid is a trisodium citrate.
    [0008]
    An adjuvant according to any one of the preceding claims, wherein (c) the inorganic oxide is a metal oxide selected from: magnesium oxide, or its salts, preferably (c) the inorganic oxide is magnesium oxide, or a mineral species composed of calcium and magnesium carbonate, such as dolomite.
    [0009]
    9. Cement composition comprising, by weight relative to the total weight of said cement composition, at least: - from 20% to 70%, preferably from 30% to 60% of a hydraulic binder, and % to 80%, preferably 40% to 70% of an adjuvant according to one of the preceding claims, - optionally from 0 to 10% of other additives.
    [0010]
    10. Refractory concrete composition comprising at least, by weight relative to the total mass of the refractory concrete composition, from 1% to 5%, preferably from 2% to 4% and in particular from 2.5% to 3.5% of a cementitious composition as defined in claim 9, and from 95% to 99%, preferably from 96% to 98% and in particular from 96.5% to 97.5% by weight. a granular mixture composed of at least one granulate and fines.
    [0011]
    11. refractory concrete composition according to claim 10, wherein the aggregate is selected from: dolomite, magnesia, alumina silicates, tabular alumina, calcined bauxites, fused alumina, synthetic mullite, spinel or a mixture thereof.
    [0012]
    12. Use of an adjuvant according to one of claims 1 to 8 for improving the drying time of a refractory concrete composition.
    [0013]
    13. Use of an adjuvant according to one of claims 1 to 8 for improving the permeability of a refractory concrete composition.
    类似技术:
    公开号 | 公开日 | 专利标题
    FR3035399B1|2019-08-09|ADJUVANT FOR CEMENT OR REFRACTORY CONCRETE COMPOSITION, USES THEREOF, AND CEMENT AND REFRACTORY CONCRETE COMPOSITIONS
    JP6312169B2|2018-04-18|Manufacturing method for lightweight ceramic materials
    CN105531238A|2016-04-27|Hydraulic binder system based on aluminum oxide
    FR2954768A1|2011-07-01|POWDER FOR DRY CHEMICAL PISA
    EP2139825B1|2010-12-01|Tempered refractory concrete block having controlled deformation
    EP2222616A2|2010-09-01|Refractory product having a doped sialon matrix
    FR2954765A1|2011-07-01|DRY POWDER
    EP3328811A1|2018-06-06|Long-workability calcium aluminate cement with hardening promoted by a temperature increase, and related use
    JP2013199427A|2013-10-03|Cast body, castable composition, and method for their production
    JP2004300026A|2004-10-28|Alumina-based porous ceramic and method of manufacturing the same
    JP5031239B2|2012-09-19|Alumina cement, alumina cement composition and amorphous refractory
    WO2015044929A1|2015-04-02|Refractory product with a siaion matrix
    Alnawafleh2009|Mechanical and physical properties of silica bricks produced from local materials
    JP2007055848A|2007-03-08|Spherical magnesia-based clinker and refractory obtained by using the same
    JP2007210805A|2007-08-23|Alumina cement, alumina cement composition and monolithic refractory
    FR3050204A1|2017-10-20|REFRACTORY CONCRETE COMPOSITIONS CONTAINING ZEOLITHIC MICROSTRUCTURES AND USES THEREOF
    FR2946642A1|2010-12-17|REFRACTORY PRODUCT WITH SIAION MATRIX, ALUMINA AND SILICON.
    同族专利:
    公开号 | 公开日
    JP2018515412A|2018-06-14|
    BR112017022898A2|2018-07-24|
    CN107531569B|2020-05-29|
    WO2016170135A1|2016-10-27|
    ES2833008T3|2021-06-14|
    EP3286156B1|2020-08-19|
    FR3035399B1|2019-08-09|
    EP3286156A1|2018-02-28|
    US20180141864A1|2018-05-24|
    KR20170140208A|2017-12-20|
    CN107531569A|2018-01-02|
    US10526247B2|2020-01-07|
    ZA201706520B|2018-11-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP2000203954A|1999-01-19|2000-07-25|Taiko Rozai Kk|Slip casting refractory composition for tapping spout cover and its lining of blast furnace, and production of tapping spout cover of blast furnace using the same|
    JP2003201183A|2001-12-28|2003-07-15|Kurosaki Harima Corp|Refractory for casting operation|
    JP2004307231A|2003-04-03|2004-11-04|Taiko Rozai Kk|Castable refractory containing aliphatic polyester fiber|
    JP2013249226A|2012-05-31|2013-12-12|Taki Chem Co Ltd|Air permeability improver for monolithic refractory|WO2019012234A1|2017-07-13|2019-01-17|Kerneos|Method for obtaining a compacted material and compacted material obtained thereby|EP1149808B1|2000-04-28|2008-05-28|Nippon Shokubai Co., Ltd.|Cement admixture and cement composition comprising this|
    US8096359B2|2006-11-17|2012-01-17|Baker Hughes Incorporated|Method of cementing using polymeric retarder|
    CN102887715B|2011-07-22|2014-07-23|宝山钢铁股份有限公司|Ladle permanent lining pouring material capable of rapid roasting|CN109455987B|2018-12-05|2021-03-09|华侨大学|Normal-temperature curing ultrahigh-performance concrete column and construction method thereof|
    US10759697B1|2019-06-11|2020-09-01|MSB Global, Inc.|Curable formulations for structural and non-structural applications|
    KR102290193B1|2020-12-24|2021-08-19|주식회사 위드엠텍|Liquid-Type Hydration Heat Reducer Composition for Concrete and Concrete Using the Same|
    法律状态:
    2016-01-15| PLFP| Fee payment|Year of fee payment: 2 |
    2016-10-28| PLSC| Search report ready|Effective date: 20161028 |
    2017-01-31| PLFP| Fee payment|Year of fee payment: 3 |
    2018-03-13| PLFP| Fee payment|Year of fee payment: 4 |
    2019-04-25| PLFP| Fee payment|Year of fee payment: 5 |
    2020-04-27| PLFP| Fee payment|Year of fee payment: 6 |
    2021-04-26| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1553723|2015-04-24|
    FR1553723A|FR3035399B1|2015-04-24|2015-04-24|ADJUVANT FOR CEMENT OR REFRACTORY CONCRETE COMPOSITION, USES THEREOF, AND CEMENT AND REFRACTORY CONCRETE COMPOSITIONS|FR1553723A| FR3035399B1|2015-04-24|2015-04-24|ADJUVANT FOR CEMENT OR REFRACTORY CONCRETE COMPOSITION, USES THEREOF, AND CEMENT AND REFRACTORY CONCRETE COMPOSITIONS|
    JP2017550794A| JP2018515412A|2015-04-24|2016-04-22|Adjuvants for cement or refractory concrete compositions, their use, and cement and refractory concrete compositions|
    US15/568,760| US10526247B2|2015-04-24|2016-04-22|Adjuvant for a cement or a refractory concrete composition, the uses thereof, and cement and refractory concrete compositions|
    BR112017022898-0A| BR112017022898A2|2015-04-24|2016-04-22|adjuvant for a hydraulic binder based composition, cement composition, refractory concrete composition and uses of an adjuvant|
    CN201680023551.7A| CN107531569B|2015-04-24|2016-04-22|Auxiliary material for cement or refractory concrete compositions, use thereof and cement and refractory concrete compositions|
    KR1020177030473A| KR20170140208A|2015-04-24|2016-04-22|Auxiliary agent for cement or refractory concrete composition, its use, cement and refractory concrete composition|
    PCT/EP2016/059048| WO2016170135A1|2015-04-24|2016-04-22|An adjuvant for a cement or a refractory concrete composition, the uses thereof, and cement and refractory concrete compositions|
    ES16722074T| ES2833008T3|2015-04-24|2016-04-22|An adjuvant for a refractory cement or concrete composition, its uses and refractory cement and concrete compositions|
    EP16722074.8A| EP3286156B1|2015-04-24|2016-04-22|An adjuvant for a cement or a refractory concrete composition, the uses thereof, and cement and refractory concrete compositions|
    ZA2017/06520A| ZA201706520B|2015-04-24|2017-09-27|An adjuvant for a cement or a refractory concrete composition, the uses thereof, and cement and refractory concrete compositions|
    [返回顶部]