• 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:
    geopolymer binder system for refractory concrete, dry refractory concrete mix, which contains the binder system, as well as the use of the mix. The present invention relates to an alkaline activated binder system for refractory castables of at least one mineral binder and a mineral activator, which in mixture with water form a hardening geopolymer, and as activator is contained a combination of at least two components of magnesium (components of mg), which react alkaline with water and, in this case, form a geopolymer reactive in a temporally different way with the binder, and the magnesium components have a different reactivity with respect to air humidity and/or with in relation to the binder. the invention furthermore relates to a dry refractory concrete mixture, which contains the binder system, as well as to the use of the mixture.
    公开号:BR112015018590B1
    申请号:R112015018590-8
    申请日:2014-01-29
    公开日:2021-06-15
    发明作者:Jennifer Werz；Bertram Kesselheim；Darina Rudert；Kai Beimdiek
    申请人:Refratechnik Holding Gmbh；
    IPC主号:
    专利说明:

    [001] The present invention relates to a geopolymer binder system for liquefied or non-liquefied refractory concrete, to a dry refractory concrete mixture, which contains the binder system, as well as the use of the mixture.
    [002] Refractory concretes are non-molded refractory products. According to DIN EN 1402-1, chapter 4.1.1, refractory castables are mixtures of refractory supplements and binder(s). They are generally supplied dry, as a mixture and, after the addition of water or another liquid and corresponding mixture, are processed into refractory concrete. They are assembled by vibration casting, vibration-free casting (self-flowing), by fanning, injecting or, if necessary, stepping on. Bonding and hardening takes place without heating. According to chapter 4.1.3, a refractory concrete mixture must contain a mass proportion of at least 2% ultrafine particles (less than one micrometer) and at least one liquefying agent.
    [003] Refractory concretes are distinguished, among others, according to their CaO content and they are affixed, consequently, in Medium-Cement (MCC) refractory castables, Low-Cement (LCC) refractory castables, refractory castables Ultra-Low-Cement (ULCC) And cement-free refractory castables (NCC). the invention refers to liquefied or non-liquefied refractory castables, free of cement. In this case, these are refractory, monolithic building materials. Cement Live means according to DIN EN 1402-1 that a maximum of 0.2% by weight of CaO, originating, for example, from cements, can be contained in the refractory concrete mixture.
    [004] There are already on the market refractory concrete mixtures, which can be dried quickly and heated quickly, to be processed only with water. The properties of the refractory castables produced from them are described in
    [005] Soudier, J.QD NCC: Quick drying on cement castables. The novel non-cementious mineral bond permitting flexible installation and extreme rapid heating up. 53rd International Colloquium on refractories 2010, Eurogress Aachen, Germany, pp. 115-118.
    [006] Makmus P. Soudier, J., Meunier, P., Badin, V.: QD NCC: Quick drying on cement castables 53rd International Colloquium on refractories 2010, Eurogress Aachen, Germany, pp. 115-118.
    [007] Feuerfesttechnik. Erhohte Anglagenverfügbarkeit und Energieeinsparung durch schnelltrocknende, zementfreie Giessbetone, messedaily GIFA 2011, Düsseldorf, p. 14.
    [008] INNOVATION & SOLUTIONS, SchnelleTrocknungsiegt bei Daimier, Refractories, Calderys Mitarbeiter Zeitung, December 2010, N. 13, p.05.
    [009] Calderys: Einfach Zeit gewinnen, messedaily GIFA 2011, Düsseldorf, p.3
    [0010] INNOVATION & SOLUTIONS, A year of innovation, Refractories, Calderys Mitarbeiter Zeitung, Juni 2010, N. 12, p.08-09.
    [0011] Soudier, J., QD NCC: Quick drying on cement castables. The novel non-cementitious mineral bond permitting extreme rapid dry out of monolithic refractory linings. UNITECR 2011, Kyoto, Japan, 1-D-17.
    [0012] Makmus P. Soudier, J., Meunier, P., Badin, V.: QD NCC: Quick dry in cement castabels implementation and performance of a novel bond system in castables for diverse applications. UNITECR 2011, Kyoto, Japan, 1-D-18.
    [0013] Oldin,J., Fowler,A., Soudier,J., Quick Dry No Cement Castables. Industrial feedback on implementation of a novel bond system in castables for foundry applications. UNITECR 2011, Kyoto, Japan, 1-D-19.
    [0014] Wagner, Dr. V., Louen, M.: Risk-Less Heating-up with Quick Dry Materials Presentation PetroCem, 7th Int., Cement Conference, 2012.
    [0015] The refractory castables described in this prior art (English: "castables") are liquefied refractory castables. Of the dry mixtures, to be prepared only with water, for these refractory concretes it is known that, in general, they are products based on Al2O3-SiO2, and contain as a main raw material component, for example, andalusite, bauxite, scale, mullit or corundum and a quick-drying, quick-heatable mineral binder system. Mixtures should generally be processed within 4 minutes, as otherwise the specified properties of the binder system, due to hydration reactions, which take place in the meantime, can no longer be guaranteed. Consequently, a shelf life of just 4 months is indicated for refractory concrete mixes supplied in big bags and 6 months as bagged products.
    [0016] From EP 839 775 B1 are known mixtures for liquefied refractory concretes, which have 30-80% by weight of a main component, with grain sizes above 74 μm (200 mesh), 1 - 30% by weight of Fine particle refractory material with grain sizes □ 74 μm (200 mesh) as well as a cement-free binder system of a so-called binder in the form of a hydratable aluminum oxide (Al2O3) and a so-called activator in the form of a magnesium oxide (MgO) quenched by calcination. These mixtures have, particularly due to the tendency of MgO to react, for example, with moisture donate to Mg(OH)2 (brucite) also have only a relatively small storage stability or shelf life, with regard to the properties of concrete. fresh and solid concrete, originally adjusted and desirable.
    [0017] From WO 99/12860 A1 a mixture is known for a liquefied reservoir chamber, which, in addition to the main component of coarse and finely divided grains, has a calcium aluminate cement and an amorphous metakaolin additive, in shape powder as a binder and microsilica as an activator. The additive must act on the bonding and hardening reactions of the cement.
    [0018] From WO 2009/0005205 A1, a binder system is known, among others, of metakaolin as a binder and an alkaline compound as an activator, which is suitable for the production of mortars for walls.
    [0019] From document US2012/0152153 A1 is known a binder system of, among others, metakaolin as a binder and an alkaline activator solution for the same of a metal hydroxide and a metal silicate, which is used for the production of normal concrete .
    [0020] In all cement-free binder-activator systems, after water ingress, a so-called hardening geopolymer is formed. A geopolymer consists of Si and Al atoms, which through oxygen atoms are linked to a polymeric network. The process of geopolymer formation extends into solution, condensation, polycondensation, as well as polymerization reactions. A very dense and durable geopolymer matrix with extremely high mechanical strength is formed.
    [0021] It is known that the processing and fresh product properties and strengths can be adjusted after hardening, for example, by the fineness of the binder and activator, the reactivity of the binder to the alkali concentration of an activator solution (pH value >9.5) and also on the interaction between binder and activator.
    [0022] But, depending on the combination, a too delayed or accelerated reaction behavior between binder and activator can occur and cause resistances of the fresh product and final product that are too small.
    [0023] Normally, at a reference temperature of 20 +/ 5°C, adjustment variables in the fresh refractory concrete product should be selected, as follows, and a water requirement as extensively reduced as possible should be targeted. , for example, by additives:
    [0024] - change point in the mixer from dry consistency to liquid or suitable for processing, within 120 seconds
    [0025] - Open processing times of fresh refractory castables of >30 minutes
    [0026] - optimal processing consistency for high densification or high strengths, that is, after the wet mixing time, within the indicated preparation water period, typical for the variety, there must be creep values, after 1 minute, >170 mm (DIN EN 1402-4)
    [0027] - secure grip after 1 hour up to 24 hours, within a temperature range of 0 - 40°C
    [0028] - fast hardening for high fresh product strength >1, particularly, >5 Mpa, after 24 hours setting time
    [0029] [0014] Compared to cement-bonded refractory castables, a gas permeability, for example, 2 to 5 times higher, for safe and accelerated drying, at an in-situ temperature rise, is a frequently required characteristic. of the geopolymer matrix. This gas permeability is generally ensured by a relatively high proportion of plastic of >0.05% by weight and optionally by the addition of porosity agents. Plastic fibers generate pores by melting on temperature rise, which increase gas permeability.
    [0030] A fundamental problem in known mixtures for liquefied refractory castables as already mentioned above - is the sensitivity to aging of the components of the very fine and reactive particulate binder system, which tend to hydrate. Hydration particularly results in a significant loss of reactivity or a change in reactivity, particularly of the binding system. This generally increases the need for water for optimal processing properties and for good creep behavior and solidifying ability. As a result, longer hardening times and lower fresh and final product strengths result.
    [0031] It is the task of the invention to create a geopolymer binder system for refractory concrete, which ensures improved storage stability for dry refractory concrete mixtures, without after a longer storage time, compared to the prior art , the originally adjusted properties of the binder system are unacceptably modified at the input of the preparation water and, with this, particularly, the processability, the setting and hardening of a previously adjusted mixture.
    [0032] This task is solved by a binder system that reacts in contact with preparation water, which presents
    [0033] As a mineral binder, for example, a finely divided, reactive aluminum silicate, particularly in the form of metakaolin and/or clay and/or tempered brick flour, and/or an alkaline earth aluminum silicate, particularly in the form of fly ash from coal and/or metallurgical sand (blast furnace slag), and/or a limestone sandstone flour and/or an amorphous silica, particularly in the form of microsilica,
    [0034] as a mineral activator, the combination of at least two Mg components, finely divided, dry, which form an alkaline solution with water, particularly in the form of MgO, produced by burning magnesite or dolomite, or by precipitation of brucite , either by thermal dissociation of magnesium chloride or magnesium sulphate or magnesium sulphide or by extraction of dolomite, in the form of so-called CCM (caustic calcinated magnesia) of MgO, and or in the form of MgO produced by sintering or melting.
    [0035] Mg components in the sense of the invention are mineral products containing MgO, which react alkaline with water, as indicated, for example, above under b), MgO products, but also mineral raw materials containing Mg, products such as olivine, forsterite, dunite, brucite, dolomite, spinel.
    [0036] In the following, exemplified, mineral binders of the binder system according to the invention are indicated.
    Aluminum silicates particularly suitable for the purposes of the invention are finely divided metakaolins, finely divided clays, finely divided brick flours, finely divided blast furnace slag and finely divided fly ash.
    [0038] Metakaolin is a highly reactive aluminum silicate puzzolan. According to the invention, it is used in very fine particle form, for example with grain sizes between 0 and 500 µm, particularly between 1 and 120 µm. The production and properties of amorphous metakaolins suitable for the purposes of the invention are described, for example, in WO 99/12860 A1 or in US patent application 08 80062 A1.
    [0039] In the context of the description of the invention, the indication "grain sizes between 0 and ex μm" means a distribution of grain sizes, determined, for example, by fractional classification with sieves with usual standardized mesh width, up to the width of x" mesh or by laser particle size and/or sedimentation of particles in a liquid according to Stokes' law.
    [0040] Metakaolin is used as a binder in the geopolymeric binder system in amounts between 40 and 99% by weight, particularly between 50 and 80% by weight, with respect to the amount of the binder system. The remainder is, in each case, at least one activator.
    [0041] Metallurgical sand is a substantially glassy silicate material. Metallurgical sands with the following composition in % by weight can be used for the purposes of the invention:

    [0042] The grain sizes of metallurgical sands are conveniently located between 0 and 12 μm. Metallurgical sands are used in amounts between 40 and 99% by weight, particularly 50 and 80% by weight, with respect to the amount of the binder system. The remainder is, in each case, at least one activator.
    [0043] Coal drag ash is a fine mineral powder, light gray to dark gray or light brown in color. Due to the high combustion temperatures, coal fly ash predominantly consists of spherical, glassy particles. Burnt out coal ash consists predominantly of silicon oxide, aluminum and iron. Furthermore, they contain several trace elements,. In addition, coal fly ash may have small proportions of residual coke.
    [0044] For the invention, fly ash can be used with the following composition in % by weight:

    The grain sizes of the fly ash are conveniently between 0 and 500 μm, particularly between 0 and 100 μm. Fly ash is used in amounts between 40 and 99% by weight, particularly between 50 and 80% by weight, with respect to the amount of the binder system. The rest is, in each case, is at least one activator.
    [0046] Other binders that can be used, particularly alkaline earth silicates, are air tempered clays, which as the main mineral may contain not only kaolinite, but also smectite/montmorrillonite or illite. For the invention, tempered clays with the following composition in % by weight can be used:

    [0047] The grain sizes of tempered clays are conveniently located between 0 and 600 μm, particularly between 1 and 120 μm. Tempered clays are used in amounts between 40 and 99% by weight, particularly between 50 and 60% by weight, with respect to the amount of the binder system. The remainder is, in each case, at least one activator.
    [0048] Amorphous silica substantially consists of spherical, very small, highly reactive particles. Varieties of microsilica with the following composition can be used for the purposes of the invention:

    [0049] The grain sizes of amorphous silica are conveniently between 0 and 100 μm, particularly between 0 and 10 μm. Amorphous silica is used in amounts between 40 and 99% by weight, particularly between 50 and 85% by weight, with respect to the amount of binder system used. The remainder is, in each case, at least one activator.
    [0050] Limestone sandstone flour is limestone sandstone ground from the construction material production site. Useable for the purposes of the invention are limestone flours having the following composition in % by weight:

    [0051] The grain sizes of limestone sandstone flours are conveniently between 0 and 100 μm, particularly between 0 and 70 μm. Limestone sandstone flours are used in amounts between 40 and 99% by weight, particularly between 50 and 80% by weight, with respect to the binder system. The remainder is, in each case, at least one activator.
    [0052] Brick flour is a recycled product with a high amorphous proportion of crushed bricks.
    [0053] Brick flours with the following composition in % by weight can be used for the purposes of the invention:

    [0054] The grain size of brick flours is conveniently between 0 and 100 μm, particularly between 0 and 70 μm. Brick flours are used in amounts between 40 and 99% by weight, particularly between 50 and 80% by weight, with respect to the amount of the binder system. The remainder is, in each case, at least one activator.
    [0055] It is within the scope of the invention to combine the at least two mentioned binders. The respective quantity of the used binder or of the at least two binders depends, in this case, on the properties to be guaranteed. The binder or combinations of the at least two binders is or are used, for example, in amounts between 40 and 99% by weight, particularly between 50 and 80% by weight, with respect to the amount of binder system.
    [0056] The following are indicated, for example, mineral activators of the binder system according to the invention.
    [0057] As activator, at least two Mg components can be used, which react alkaline with water. Mg components containing MgO are, for example, CCM or MgO quenched by calcination, sintered or melted. These MgO products are obtainable in the market. They are, in particular, calcined or burnt products of Magnesite or brucite. Furthermore, as MgO-rich spinel Mg component, magnesium silicates such as olivine, forsterite, dunite, Mg-containing additives such as MgO-containing sodium phosphate, brucite and/or dolomite can be used.
    [0058] It is known that different MgO products, calcined or extinct by calcination, can react, in general, with different speed in contact with moisture, to brucite (Mg(OH)2) and that the formation of brucite negatively influences the capacity reaction rate of MgO with respect to water and the binding component of the binding system.
    [0059] First, the long-term modification of the reaction capacity of the Mg component containing MgO can be tested by an independent measurement method, developed in-house, for example, in a climate-controlled cabinet, at a certain temperature and a certain humidity air and at specified time intervals. After, in each case, a certain application time, the water absorption is measured and, therefore, the formation of brucite. Conveniently, this measurement method is performed or standardized as follows:
    [0060] Samples of MgO material to be tested are previously weighed and stored in the climate-controlled cabinet, at a certain temperature, for example, between 30 to 35°C and at a relative humidity. determined from, for example, 80 to 85%, for example, 1 to 168 hours. After predetermined storage times, in each case sample material is removed and, for example, dried for 1 hour in a drying cabinet at a temperature of, for example, 110°C and weighed again. The weight gain formed by hydration is stoichiometrically calculated on the amount of brucite.
    [0061] After finding the time-dependent brucite formation, according to the independently developed standardized climate-controlled cabinet method, it can be verified with the MgO material samples, which contain brucite in different amounts, from the cabinet test empirically acclimatized the reaction capacity with the binder and, from there, reach a conclusion about the storage capacity of the binder system in months, and the reaction capacity can be controlled, for example, through the switching point in the wet mixing process, or measurement of extension, or sticking behavior according to the cup test or the ultrasound method, or finding the strength of the fresh product according to DIN EN 1402, Part 6.
    [0062] The responsiveness of the binder system was preferably tested with the known extent measurement process. This method of measuring extension is carried out within the scope of the invention according to DIN EN 1402-4, Ungeformte feuerfeste Erzeugnisse - Teil 4: Bestimmung der Konsistenz von Feuerbetonen; German version EM 1402-4; 2003.
    [0063] With knowledge of the formation of brucite, it would be possible to adjust the possible storage time with a single tested MgO product. But since MgO products, which ensure a longer shelf life of the binder system, have caused relatively poor processability and poor setting and hardening, this measure does not necessarily lead to the goal.
    [0064] The inventors found that by combining at least two Mg components, particularly at least two MgO products, with different reactivity with respect to moisture or brucite formation or reaction with a binder in a binder system according to the invention or in a refractory concrete mixture according to the invention it can be guaranteed that for a longer storage time than hitherto of, for example, about 6 months, the processability, the creep, setting and hardening behavior, that a binder system or a mixture, which contains the binder system, guarantees initially, after production, to remain practically unchanged up to a predetermined maximum storage time of, for example, >6 months.
    [0065] According to the invention, in this case, the combination of, for example, at least two caustic MgO, with temporally different moisture absorption and brucite formation, is used as an activator, with a CCM being more reactive and therefore it reacts more quickly, and the other CCM is less reactive and reacts more slowly. Other combinations have, for example, the combination of at least one more reactive caustic MgO and at least one less reactive calcined MGO, or for example. the combination of at least one more reactive caustic MgO and at least one less reactive spinel or the combination of a more reactive caustic MgO and at least one raw material or product containing a less reactive Mg, for example, forsterite or olivine or another silicate magnesium such as dunite or serpentinite.
    [0066] The invention comprises, for example, the following activator combinations:


    [0067] An activator combination according to the invention is mixed with at least one binder of the type indicated above and measured, for example, the change point, the measure of extension or the creep value after 1 minute and 25 minutes , as well as the setting behavior and the hardening properties, depending on the storage time. In order to determine a storage stability, some test tests must be carried out, which include the supplements, addition materials and additives of the refractory concrete mixture, in each case used.
    [0068] For example, a combination according to the invention of MgO products can be determined as follows:
    [0069] A more reactive caustic MgO is used, with an average grain size d50 = 5 µm, a high MgO purity > 98% by weight, and a high brucite formation at 30°C and 80% relative humidity of the air >5% by weight after 24 hours. In addition, a less reactive caustic MgO is used, with an average grain size of d50 = 50 µm, a lower MgO purity of 96% by weight and a lower relativity for brucite formation, at 30°C and 80% of air humidity of < 3% after 24 hours.
    [0070] With the more reactive CCM, the less reactive CCM and a mixture of the two CCMs, in the ratio of 1:1, the following refractory concrete mixtures were produced, in each case of a basic Supplement mixture: 66.5% by weight of melting corundum Additive: 25% by weight of alumina flour 4.5% by weight of microsilica Binder: 2.5% by weight of metakaolin and 1.50% by weight of more reactive CCM 1.50% by weight weight of less reactive CCM 1.50% by weight of a mixture of the two CCMs in a weight ratio of 1:1
    [0071] To these mixtures were added 5.5% by weight of water and the mixtures were mixed and then the creep value was determined according to DIN EN 1402-4, after one minute, as well as the pressure resistance cold test specimens produced from the mixture, after storage for 24 hours at 20°C.
    [0072] The result is shown by Figure 1 for the creep value depending on the amount of brucite formation of the CCMs or the combination of CCMs and Figure 2 shows the result for the pressure resistance. Figure 1 shows the change in creep values (1 min), depending on the proportion of new brucite formed using the less reactive CCM, the reactive CCM, as well as a mixture of the two activators. Figure 2 shows the modification of cold pressure resistance, after 24 h of hardening time, depending on the proportion of new brucite formed, using the less reactive CCM and the reactive CCM, as well as the mixture of the two activators.
    [0073] The creep values characterize the processability of the mixtures, which should be kept for months, if possible, above 170 mm. Likewise, the resistance to cold pressure must be maintained, which is an indication of the final resistances obtained.
    [0074] From Figure 1 it can be seen that by the combination of CCMs, acceptable fluence values can be guaranteed, from the beginning, to relatively high brucite values (9% by weight).
    [0075] From Figure 2 it can be seen that the pressure resistance remains maintained by the combination of CCMs, at a relatively high level, at high brucite values.
    [0076] The example shows the effect of a combination of CCMs with a particular binder. The same results are obtained with other combinations of activators and other binders, which is plausible for the technician.
    [0077] The following combinations of MgO components have been found to be stable for a particularly long time against property changes:
    [0078] Next, exemplified compositions for refractory concrete mixtures are indicated in % by weight, with respect to the total mixture = 100% by weight. a) Binder system 1.01 - 37.5, particularly 3.0 to 22.5, with the following amounts of binder/activator mixtures in % by weight: Binder: 1 - 15, particularly 2 - 15 Activator : 0.01 - 22.5, particularly 1.0 - 7.5 b) Mineral supplements 62.5 - 98.99, particularly 87.5 - 97.0 of at least one supplement with usual grain distribution of flour fraction to coarse grain eg up to 15 mm, eg selected from the following group: - light supplements such as vermiculite, perlite, swelling clay - refractory brick, rich in alumina/acid - andalusite/silmania - mullite - bauxite - calcium hexa-aluminate - sintered corundum - fused corundum (BFA, 94-97% Aç2O3) - fused corundum (WFA, >99% Al22O3) - raw materials containing zirconium oxide (Zirconia, AZs) - magnesia - forsterite (olivine) - doloma - silicon carbide - zirconium (zirconium silicate) - quartz sand - spinel - graphite, coke, carbon black - cro ore mo, chromium oxide c) Finely divided mineral additives - clay binder - microsilica 0-15, particularly 1-10 0-9, particularly 3-5 - alumina flour 0-30, particularly 5-20 - cement alumina (15-32% CaO) 0-0.6, particularly 0.1-0.3 - alumina fusion cement 0-0.5, particularly 0.1-0.25 (32-39% of CaO) - Portland cement (60-72% CaO) 0-0.25, particularly 0.10.15d) Additives - additives such as agents 0-0.5, particularly 0.1-0.15 of liquefaction, setting regulators - aluminum hydroxide 0-0.5 0-0.5 0-3.0 0-0.3, particularly 0.1-0.15
    [0079] The invention is characterized by the following characteristics:
    [0080] The invention contains an alkaline activated binder system for refractory castables of at least one mineral binder and a mineral activator, which in mixture with water form a hardening geopolymer, and as activator is contained a combination of at least two components of magnesium (Mg components), which react in an alkaline way and, in this case, form a reactive geopolymer in a temporally different way, and the Mg components have a different reactivity with respect to air humidity, due to the fact that a Mg component, at a given time, at a given relative air humidity, binds more moisture or water than
    [0081] It is advantageous when the activator contains at least one MgO product as a Mg component.
    [0082] Furthermore, it is advantageous when the activator has at least one MgO product and at least one Mg component, which reacts alkaline with water, has no MgO product, or consists of the two Mg components, which the other component of Mg and/or present a different reactivity, which changes temporally, in relation to the binding agent.
    [0083] It is convenient when the activator only presents MgO products as Mg components or only consists of MgO products.
    [0084] It is particularly advantageous when the activator has at least two caustic MgO as Mg components, particularly, it consists of two caustic MgO.
    [0085] Within the scope of the invention it was determined that the activator combinations should be selected from the following group of Mg components: caustic MgO, calcined MgO, in the form of fused and/or sintered magnesia, spinel with excess MgO, spinel, brucite, magnesium silicate such as forsterite, olivine, dunite, serpentinite, MgO containing additive such as sodium phosphate containing MgO.
    [0086] The binder system advantageously contains as binder at least one finely divided aluminum silicate, reactive with the activator, preferably amorphous, more precisely, selected from the group metakaolin, tempered alumina, brick flour, fly ash of coal, metallurgical sand. Furthermore, they can be used very well as a binder of limestone sand flour and amorphous silica.
    [0087] It is advantageous when the binder system contains between 0.01 and 22.5% by weight, particularly between 1.0 and 7.5% by weight of activator and between 1 and 15, particularly between 2 and 15% by weight of binder.
    [0088] In a refractory concrete mixture, a binder system according to the invention works without problems if the refractory concrete mixture contains at least one supplement of one or more refractory materials, with usual grain distribution for refractory concrete mixtures . Binder system should preferably be contained in the following amounts by weight: 1 - 15, particularly 2 - 15 of binder, 0.01 - 22.5, particularly 1.0 - 7.5 of activator.
    [0089] It is advantageous to select the supplements listed in the description and use at least one of them, more precisely, preferably in amounts between 62.5 and 98.99, particularly between 87.5 and 97.0% by weight. The refractory castable mixtures according to the invention can, furthermore, have at least one supplement and at least one additional agent, in each case, selected from the groups indicated in the description, preferably in the amounts indicated in the description.
    [0090] Refractory concrete mixes are preferably used in the installation sectors of the steel industry, for example, steel casting ladle, distributor, steel casting ladle rim, drilled bricks, wash cone by gas, furnace cover E, as well as furnace aggregates for crude iron production, eg blast furnace, main chute, iron chute, slag chute, tipping chute and crude iron treatment, eg crude iron ladles. smelting of raw iron, raw iron mixtures, as well as for transporting raw iron, for example, particularly for the delivery of torpedo transport containers, particularly torpedo pan nozzles, in addition, for injection treatment regions previously worn out of a torpedo transport container. Furthermore, refractory concrete mixes find application in kiln aggregates in the aluminum industry, for example, in aluminum smelting furnaces, aluminum treatment furnaces or furnaces for heat conservation, in the bath sector, as well as in walls sides of the upper furnace, the roof delivery, the ramps sector, the filling pit and the melting bridges sector. In waste incineration plants, for example, in the filling region, on side walls and roofs, in electric power plants, predominantly in the region of heating boilers and flue gas breathing wells, as well as in foundry plants For example, for the delivery of monolithic ladles, for the delivery of casting nozzles and chute systems, the refractory castables according to the invention can be used particularly advantageously because of their superior properties.
    [0091] The refractory concrete mixtures according to the invention are also preferably used in sectors of the clinker production facility of the cement industries, particularly in zones before, in one or after a cement kiln , in which, for example, a first drying of the monolithic delivery takes place by the first hot clinker. The zones extend, for example, in the output ring, surrounding ring to the wear benches in the cooling device.
    权利要求:
    Claims (26)
    [0001]
    1. Dry alkaline binder system for dry refractory concrete mixes, composed of at least one mineral binder and one mineral activator, which form a hardening geopolymer in mixture with water, characterized by the fact that a combination of at least two magnesium components , which react with water in an alkaline way and, in this case, reactively form the geopolymer with the binder in a different way, in terms of time, is contained as an activator, in which the magnesium components comprise a different reactivity with respect to the moisture of the air and with respect to the binder, wherein the binder system presents, as a binder, at least one amorphous finely divided aluminum silicate that is reactive with the combination of activator from the metakaolin group, tempered alumina, brick flour, and/ or an alkaline earth aluminum silicate from the group of coal fly ash, metallurgical sand, and/or coal fly ash and/or metallurgical sand a, and/or an amorphous silica, wherein the activator combination is selected from the following group of magnesium components: Caustic MgO, calcined MgO in the form of fused and/or sintered magnesia, spinel with excess MgO, spinel, brucite, dolomite, magnesium silicates such as forsterite, olivine, dunite, serpentinite, additives containing MgO in the form of sodium phosphate containing MgO.
    [0002]
    2. Binder system according to claim 1, characterized in that the activator contains at least MgO product in the form of caustic MgO, fused or sintered magnesia as a magnesium component.
    [0003]
    3. Binder system according to claim 2, characterized in that the activator has at least one MgO product in the form of caustic MgO, fused or sintered magnesia as a magnesium component and at least one magnesium component, which reacts alkaline with water and has no MgO, or the activator consists of the two Mg components.
    [0004]
    4. Binder system according to claim 2, characterized in that the activator consists only of MgO products.
    [0005]
    5. Binder system according to any one of claims 2 to 4, characterized in that the activator has at least two caustic MgO compounds as magnesium components.
    [0006]
    6. Binder system according to claim 5, characterized in that the activator consists of two caustic MgO compounds.
    [0007]
    7. Binder system according to any one of claims 1 to 5, characterized in that it contains 40 to 99% by weight of binder.
    [0008]
    8. Binder system according to claim 7, characterized in that it contains 50 to 80% by weight of binder.
    [0009]
    9. Binder system according to claim 7, characterized in that it contains 80 to 99% by weight of binder.
    [0010]
    10. Dry refractory concrete mixture, which contains at least one supplement composed of refractory material, characterized in that the refractory concrete mixture contains at least one binder system, which with water forms a geopolymer, as defined in any of the claims 1 to 9.
    [0011]
    11. Mixture of refractory concrete, according to claim 10, characterized in that the mixture of refractory concrete contains at least one system of binder in the following amounts in % by weight: 1 to 15 of binder, 0.01 to 22.5 of activator.
    [0012]
    12. Mixture of refractory concrete, according to claim 11, characterized in that the mixture of refractory concrete contains at least one system of binder in the following amounts in % by weight: 2 to 15 of binder, 1.0 to 7.5 activator.
    [0013]
    13. Refractory concrete mixture, according to any one of claims 10 to 12, characterized in that the refractory concrete mixture contains at least one supplement selected from the following group: - light supplements, - refractory brick rich in alumina/acid , - andalusite/silimanite, - mullite, - bauxite, - calcium hexaaluminate, - sintered corundum, - fused corundum (BFA, 94 to 97% Al2O3), - fused corundum (WFA, >99% Al2O3), - materials raw materials containing zirconium oxide (Zirconia, AZs), - magnesia, - forsterite (olivine), - doloma, - silicon carbide, - zirconium (zirconium silicate), - quartz sand, - spinel, - graphite, coke, carbon black, - chromium ore, chromium oxide.
    [0014]
    14. Mixture of refractory concrete, according to claim 13, characterized in that the mixture of refractory concrete contains the at least one supplement in amounts between 62.5 and 98.99% by weight.
    [0015]
    15. Mixture of refractory concrete, according to claim 14, characterized in that the mixture of refractory concrete contains the at least one supplement in amounts between 77.5 and 97.0% by weight.
    [0016]
    16. Mixture of refractory concrete, according to any one of claims 13 to 15, characterized in that the light supplement is vermiculite and/or perlite and/or swelling clay.
    [0017]
    17. Mixture of refractory concrete, according to any one of claims 10 to 16, characterized in that it contains at least one finely divided mineral additive.
    [0018]
    18. Mixture of refractory concrete, according to claim 17, characterized in that the at least one finely divided mineral additive is selected from the following group in the quantities indicated in % by weight: - binding clay: up to 15, - alumina: up to 30, - alumina cement (15 to 32% CaO): up to 0.6, - alumina fusion cement (32 to 39% CaO): up to 0.5, - Portland cement (60 to 72 % CaO): up to 0.25.
    [0019]
    19. Mixture of refractory concrete, according to claim 18, characterized in that the at least one finely divided mineral additive is contained in the quantities indicated in % by weight: - binding clay: 1 to 10, - alumina flour: 5 to 20, - alumina cement (15 to 32% CaO): 0.1 to 0.3 - alumina fusion cement (32 to 39% CaO): 0.1 to 0.25, - Portland cement (60 to 72% CaO): 0.1 to 0.15.
    [0020]
    20. Mixture of refractory concrete, according to claim 10 to 19, characterized in that it comprises at least one additive.
    [0021]
    21. Mixture of refractory concrete, according to claim 20, characterized in that the at least one additive is selected from the following group: - additives such as liquefying agents, binding regulators, - aluminum hydroxide, - forming pores, - fine steel fibers, - plastic fibers.
    [0022]
    22. Mixture of refractory concrete, according to claim 21, characterized in that the at least one additive is contained in the amounts indicated in % by weight: - additives such as liquefying agents, binding regulators: up to 0.5 , - aluminum hydroxide: up to 0,5, - pore former: up to 0,5, - fine steel fibers: up to 3,0, - plastic fibers: up to 0.3.
    [0023]
    23. Mixture of refractory concrete, according to claim 22, characterized in that the at least one additive is contained in the quantities indicated in % by weight: - additives such as liquefaction agents, binding regulators: 0.1 to 0.15, - aluminum hydroxide: up to 0.5, - pore former: up to 0.5, - fine steel fibers: up to 3.0, - plastic fibers: 0.1 to 0.15.
    [0024]
    24. Use of a refractory concrete mixture as defined in any one of claims 10 to 23, characterized in that the refractory concrete mixture is used in steel industry installations, in kiln aggregates for the production of raw iron and raw iron treatment, or in raw iron transport aggregates, or for treatment injections of worn regions in such facilities or aggregates.
    [0025]
    25. Use of a refractory concrete mixture as defined in any one of claims 10 to 23, characterized in that the refractory concrete mixture is used in kiln aggregates in the aluminum industry.
    [0026]
    26. Use of a refractory concrete mixture as defined in any one of claims 10 to 23, characterized in that the refractory concrete mixture is used in production facility and clinker sectors of the cement industry.
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    同族专利:
    公开号 | 公开日
    SI2951133T1|2022-01-31|
    BR112015018590A2|2017-07-18|
    EP2951133A1|2015-12-09|
    US20150376060A1|2015-12-31|
    RU2664723C2|2018-08-22|
    MX2015009947A|2015-09-29|
    RU2015133906A|2017-03-10|
    DE102013001927A1|2014-08-07|
    EP2951133B1|2021-11-03|
    DE202013011896U1|2014-09-16|
    DE102013001927B4|2019-01-17|
    KR20150118969A|2015-10-23|
    WO2014118242A1|2014-08-07|
    US10029945B2|2018-07-24|
    KR102078660B1|2020-02-18|
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-22| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-08| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-04-27| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-15| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/01/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102013001927.3A|DE102013001927B4|2013-02-04|2013-02-04|Geopolymer binder system for Feuerbetone, dry Feuetonetonversatz containing the binder system and the use of the offset|
    DE102013001927.3|2013-02-04|
    PCT/EP2014/051733|WO2014118242A1|2013-02-04|2014-01-29|Geopolymer-binder system for fire concretes, dry fire concrete mix containing the binder system and also the use of the mix|
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