WO2017198377A1 - Zur elastifizierung von grobkeramischen feuerfesterzeugnissen geeignete feuerfeste spinellgranulate, verfahren zu ihrer herstellung und ihre verwendung - Google Patents
Zur elastifizierung von grobkeramischen feuerfesterzeugnissen geeignete feuerfeste spinellgranulate, verfahren zu ihrer herstellung und ihre verwendung Download PDFInfo
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- WO2017198377A1 WO2017198377A1 PCT/EP2017/056998 EP2017056998W WO2017198377A1 WO 2017198377 A1 WO2017198377 A1 WO 2017198377A1 EP 2017056998 W EP2017056998 W EP 2017056998W WO 2017198377 A1 WO2017198377 A1 WO 2017198377A1
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Definitions
- the invention relates to the refining of coarse ceramic, in particular basic, refractory products suitable refractory spinel elastomer granules, a process for their preparation and their use in spinelelastifizieriferous, coarse ceramic, especially basic refractory products.
- Ceramic refractory products are based on refractory materials, eg. B. on basic refractory materials.
- Refractory basic materials are materials in which the sum of the oxides MgO and CaO clearly outweighs. They are z. B. in Tables 4.26 and 4.27 in "Paperback refractory materials, Gerald Routschka, Hartmut Wuthnow, Vulkan-Verlag, 5th edition" listed.
- Elasticizing spinel granules - hereinafter also referred to as "spinel elastomers” or “elastifiers”, which are usually used in the form of coarse granules - in a coarse ceramic, as a so-called main component at least one refractory mineral refractory material granules, z.
- spinel elastomers or "elastifiers”
- main component at least one refractory mineral refractory material granules, z.
- basic, refractory products are mixed with a suitable content of the refractory products, randomly distributed in the refractory product structure, granular present, compared to the main component other mineral composition having refractory material granules, which in comparison to the main component z.
- the main component at least one granular, z. B. basic, refractory mineral material.
- elastifiers are, for example, MA spinel, hercynite, galaxite, pleonast but also chromite, picrochromite. They are z. B. in the above-mentioned paperback in Chapter 4.2 in connection with various, z. As basic coarse ceramic refractory products described.
- Usual grain sizes of granular spinel elastomers are known to be mainly z. B. between 0 and 4 mm, in particular between 1 and 3 mm.
- the grains of the main components of the refractory products of refractory, z. B. basic materials are known mainly z. B. between 0 and 7 mm, in particular between 0 and 4 mm.
- each main component may also contain flour or powder fractions of up to, for example, 35% by weight, in particular 20% by weight and subordinately coarser, because these are industrially produced products which are only available with Limited accuracies are generated.
- Crude ceramics refractory products are mainly shaped and unformed ceramically fired or unfired products produced by a heavy clay manufacturing process using refractory component grain sizes, e.g. B. to 6 mm or 8 mm or 1 2 mm are made (Paperback, page 21/22).
- the refractory main component - also called Resistor - or the main refractory components of such z.
- basic refractory products essentially ensure the desired fire resistance and mechanical see or physical and chemical resistance, while the elastifiers in addition to their elasticizing effect also at least supportive of the mechanical and thermomechanical properties, but also possibly the corrosion resistance and a chemical resistance z. B. to ensure against alkalis and salts.
- the proportion of the main refractory component predominates, ie it is more than 50% by mass in the refractory product, so that the content of elastifier is generally below 50% by mass.
- Refractory elastifiers - also called micro crack images - are used for heavy clay fireproof products such. B. in DE 35 27 789 C3, DE 44 03 869 C2, DE 1 01 1 7 026 B4 described. It is therefore refractory materials that the resistance of the structure of the refractory, z. B. increase basic products against mechanical and thermo-mechanical stresses, in particular by reducing the modulus of elasticity and resistance to chemical attack, eg. B. against slag attacks, as well as salt and Alkalalienangriffe at least not worsen. As a rule, cause of the elastification microstructural disorders such as tensions and / or microcracks, which can lead to the fact that externally registered voltages can be reduced.
- alumina-containing basic refractory products for use z. B. in the cement, lime or dolomite industry at high operating temperatures around 1, 500 ° C generally have sufficient mechanical and thermo-mechanical properties. These products are usually elasticized by the addition of alumina and / or magnesium aluminate spinel (MA spinel) to calcined magnesia. Such magnesia-based refractory products require low levels of calcium oxide (CaO), which is only possible with well-prepared, expensive raw materials. In the presence of calcium oxide, aluminum oxide and MA spinel form CaO-Al 2 O 3 melts and thus adversely affect the brittleness of the ceramic products. In addition, arise in industrial furnace units, eg.
- hercynite FeAI 2 0 4
- FeAI 2 0 4 hercynite
- refractory products for the combustion zones in cement rotary kilns which have a significantly improved reactivity due to the iron content of the elastifier and in the case of synthetic hercynite (DE 44 03 869 C2 ) or iron oxide-aluminum oxide granules (DE 1 01 1 7 026 A1) are added to the ceramic batch mass of the refractory product.
- the invention according to DE 1 01 7306 B4 describes an alternative to hercynite in that a synthetic refractory material of the pleonastic spinel type having the mixed crystal composition (Mg 2+ , Fe 2+ ) (Al 3+ , Fe 3+ ) 2 0 4 and MgO contents of 20 to 60 wt .-% is proposed.
- mineral phases such as periclase (MgO), magnesiowüstite (MgO ss) and magnesioferrit (MgFe 2 0 3 ), which, as inherent constituents, influence the coefficient of linear expansion of the spinel and adversely affect the spinel Brittleness of spinel-containing refractory product.
- Hercynit and Pleonast have an annealing gain of up to 4% and up to 2%, respectively. Under oxidizing conditions and corresponding temperatures, the crystal lattice of the hercynite breaks down. In the case of Pleonast, the magnesia resistance is converted into magnesia ferrite.
- the object of the invention is to provide a lower oxidation potential or oxidation-resistant, especially in basic refractory products better and more durable elastifying acting spinel, preferably in addition to the good elastification and a good thermochemical and thermomechanical resistance and the same elastification in comparison z. B.
- the object of the invention is also to provide coarse ceramic basic refractory products and uses therefor which are superior to the known coarse ceramic, in particular basic refractory products with respect to oxidation resistance as well as thermochemical and thermomechanical resistance and buildup in situ by a content of at least one Elastifizierergranulats of the type according to the invention.
- the invention relates to by a sintering process in neutral, especially oxidising forming atmosphere, particularly in an air atmosphere made Spinellelastifizierergranulate with selected compositions of spinels in the ternary system MgO Fe 2 03-AI 2 03.
- the sintering process is compared with the melting process much more energy efficient feasible.
- the sintering process brings about the surprising effect, in comparison to the melting process, that an oxidation-resistant spinel monophase forms practically without secondary phases, which is also resistant in situ and thus exposed to at least one spinel elasticizer according to the invention in an oxidizing atmosphere.
- B. in the form of granules containing coarse ceramic, especially basic refractory product remains stable and ensures its elasticity and also supports its thermochemical and thermomechanical resistance.
- the spinel monophase leads to a very good formation of deposits in a cement rotary kiln.
- MgO 12 to 19.5, especially 15 to 17 wt .-%
- Fe 2 0 3 and Al 2 0 3 in the ratio range Fe 2 0 3 to Al 2 0 3 between 80 to 20 and 40 to 60 wt .-%.
- the field of the ESS according to the invention is as follows: The minimum and maximum MgO content was within the scope of the invention with 12 wt .-% and 19.5% by weight determined.
- the lateral boundaries of the ESS field are in each case lines of constant Fe 2 O 3 / Al 2 O 3 ratios (% by weight).
- these boundaries represent a section of the connecting line from the apex of the triangle (MgO) to the base of the triangle.
- the above ratios are the coordinates of the points of the base of the triangle.
- the mixed crystals each contain a Fe 2 0 3 and Al 2 0 3 content in solid solution from the respective specified limited areas such that a total composition to Calculated 1 00 wt .-%.
- the compositions are thus always in the spinel field range of the ternary system with respect to MgO between 1 2 and 1 9.5 wt .-% MgO.
- Particularly suitable as elasticizer are spinels from the inventive composition field region, which in granular form Kornrohêtn of at least 2.95, particularly at least 2.99, preferably at least 3.0 g / cm 3, in particular up to 3.2 g / cm 3, most especially up to 3.7 g / cm 3 , measured according to DIN EN 993-1 8.
- These elastifiers optimally elasticize in particular coarse ceramic basic refractory products offset therewith.
- Monophasic for the purposes of the invention means that in the technical spinel mixed crystals according to the invention no, but at most less than 5, especially less than 2 wt .-% secondary phases, for. B. originating from impurities of the starting materials.
- the grain compressive strengths of the grains of the elastification granules are between 20 MPa and 35 MPa, in particular between 25 MPa and 30 MPa (measured in accordance with DIN EN 1 3055 - Appendix C).
- the inventive granular spinel elastomers are preferably prepared and used with the following grain distributions (determination by sieving):
- the grain sizes are used with normal, customary grain distributions, in particular Gaussian grain distributions, or with certain conventional grain fractions in which certain grain fractions are absent (default grain size), as is common practice.
- the monophasic sintered spinel elastomers according to the invention are clearly identifiable by means of X-ray diffractometry as exclusively monophasic present, as will be shown below.
- the spinel monophases are analyzable as exclusively present in light micrographs and quantitatively the composition of the mixed crystals or monophases can be determined by X-ray fluorescence elemental analysis, e.g. with an X-ray fluorescence spectrometer z. B. with the type Bruker S8 Tiger.
- Fig. 1 in wt .-% is in the ternary ternary system MgO-Fe 2 03-Al 2 03 according to the invention discovered composition field region of fizierer as an elastic appropriate monophasic Spinellmischkristalle as ESS limited rectangle, while the composition Field of the known pleonastic Spinellelastifizierer drawn limited rectangle as pleonaste is.
- the typical spinel elasticizer composition of the commonly used hercynite is characterized as a limited rectangle Hercynite.
- the invention thus relates to sintered iron-rich spinels which are within the ternä- ren system MgO Fe 2 03-AI 2 03 and neither the spinels of Hercynit- are still made in which the pleonaste group.
- the respective spinel product consists only of a synthetic mineral monophase and, due to the predominant existence of trivalent iron (Fe 3+ ), has no or hardly any oxidation potential.
- Reactive secondary phases as z. B. are often present in pleonastic or hercynitic spinel types are not present or not detectable by X-ray and can not affect the performance of refractory products containing the spinel products according to the invention in the spinel products according to the invention.
- the monophase sintered spinels of the ternary material system MgO-Fe 2 O 3 -Al 2 O 3 used according to the invention in granular form differ essentially from the pleonastic spinels by the valence of the cations and by lower MgO contents.
- An excess of magnesium which occurs only in the high temperature range, does not show up in the ternary system of iron-rich spinel used in the invention, but the latter consists only of a mineral monophase thanks to the absence of secondary phases such.
- the monophasic spinels used according to the invention are therefore superior to the pleonastic spinel because the abovementioned secondary phases are missing, have the coefficients of linear expansion close to those of magnesia and thus have only a slight elasticizing effect.
- the spinels used according to the invention can be prepared by a simple process which, after the preparation of three raw material components, provides for a sintering process at temperatures which are moderate compared to melting processes.
- z. B. from a mixture of sintered magnesia, naturally occurring iron oxide and / or mill scale and alumina after sintering forms a mineral monophase, wherein caustic magnesia, fused magnesia and metallurgical bauxite can also be used as starting materials.
- the structural peculiarity of spinels employed in this invention as granules allows to include oxides such as Al 2 0 3 or Fe 2 0 3 in solid solution in the crystal, so that the end members represented by ⁇ - ⁇ 2 0 3 or Y-Fe 2 0 3 become.
- This circumstance allows the preparation of the mineral monophase in the ternary ternary system MgO-Fe 2 0 3 -AI 2 0 3 , whose electrical neutrality is ensured by cation defects in the spinel crystal lattice.
- the difference in linear expansion coefficients of two or more components in a ceramic refractory product when cooled after a sintering operation results in the formation of microcracks mainly along the grain boundaries, thus increasing its ductility or reducing brittleness.
- the blending, shaping and sintering of burnt magnesia in admixture with spinel granules of the present invention using conventional production techniques results in basic refractory materials having reduced brittleness, high ductility and excellent alkali resistance which is superior to particularly basic products, sinter or melt hercynite or sintered or enamel bulk as an elasticizer component.
- the iron-rich surface of inventive refractory products containing spinel granules causes the formation of the brownmillerite melting at 1 .395 ° C., which leads to a very good deposit formation and thus to a very good protection of the refractory material against thermomechanical stress by the kiln Contributes furnace.
- the production of the sintered spinel used according to the invention as an elasticizer is described by way of example below.
- this is an iron-rich sintered spinel from the composition field ESS according to FIG. 1 in the three-substance system MgO-Fe 2 O 3 -Al 2 O 3 (in the following the sintered spinel is also referred to as ESS).
- Starting materials are at least one magnesia component, at least one iron oxide component and at least one alumina component.
- the magnesia component is in particular a high-purity MgO component and in particular fused magnesia and / or sintered magnesia and / or caustic magnesia.
- the MgO content of the magnesia component is in particular above 96, preferably above 98 wt .-%.
- the iron oxide component is in particular a high-purity Fe 2 O 3 component and in particular natural or processed magnetite and / or hematite and / or mill scale, a by-product of iron and steel production.
- the Fe 2 0 3 content of the iron oxide component is in particular more than 90, preferably more than 95 wt .-%.
- the alumina component is in particular a high-purity Al 2 O 3 component and in particular alpha and / or gamma alumina.
- the Al 2 0 3 content of the aluminum component is in particular more than 98, preferably more than 99 wt .-%.
- These starting materials preferably have a fineness of fineness with particle sizes ⁇ 1, in particular ⁇ 0.5 mm. They are intimately mixed until a homogeneous to nearly homogeneous distribution of the starting materials in the mixture is present. It is expedient to mix the flours in a grinding unit and to apply a grinding energy which increases the fineness and consequently increases the reactivity of the flour particles for a sintering process. For example, the grinding and / or mixing in a z. B. a ton of millbase receiving ball mill or roll mill within z. B. 20 to 40 minutes. By simple mixing-mixing experiments, an optimization of the grinding-mixing process for a reaction activation of the starting materials for the sintering process can be determined.
- the meal is z. B. 1 5 to 30, especially 20 to 25 minutes.
- the optimal fineness of the sintering reaction and mixture of the starting materials can also be advantageously produced in the grinding aggregate by grinding, by at least one granular starting material having grain sizes z. B. over 1, z. B. 1 to 6 mm is used, which is comminuted very fine during the grinding. After mixing or grinding, the fineness of the mixture z. B. 90 wt .-% ⁇ 100 ⁇ , in particular ⁇ 45 ⁇ amount.
- the mixture of the starting materials is then in neutral or oxidizing atmosphere, in particular under air supply z. B. 3 to 8, in particular 4 to 6 hours z. B. sintered at temperatures between 1 .200 ° C and 1 .700 ° C, in particular between 1450 and 1550 ° C until reaching the desired monophase, wherein an ESS solid is formed or more solids are formed. It is then cooled and the solid crushed, z. B. with cone or roll crushers or the like. Crushing unit, so that usable as elastifiers, broken granules are formed. Subsequently, the crushed, granular material z. B. divided by sieving into certain granular ESS granule fractions. For sintering, e.g. Rotary kilns, bogies, shaft or tunnel ovens are used.
- sintering e.g. Rotary kilns, bogies, shaft or tunnel ovens are used.
- a compression of the mixture for.
- granulating, pressing or vibrating before sintering Preferably, from the mixture compressed, in particular pressed moldings, for.
- pressed moldings for.
- the granules have expediently a volume between 10 and 20 cm 3 , in particular between 12 and 15 cm 3 and densities between 2.90 and 3.20 g / cm 3 , in particular between 3.00 and 3.10 g / cm 3 .
- the density is determined according to DIN EN 993-18. Pressed moldings have z. B. volumes between 1 .600 to 2,000 cm 3 .
- the compaction of the mixture accelerates the sintering reactions and favors the extra-phase freedom of the achievable monophases of the ESS.
- compositions are characterized by the drawn points in the demarcated fields in Fig. 1st ,
- compositions at points 1, 2, 2-1 correspond to compositions of the ESS for the invention (hereinafter also referred to as composition according to the invention or spinel or inventive region according to the invention).
- compositions at points 5, 5-1, as well as at points 6-1, 6-2, 6-3, 6-4, which are "6" in the drawn circle, correspond to pleonastic compositions according to DE 101 17 029 B4 ,
- the weighed starting materials were ground and mixed for 4 minutes in a rotary disk mill at 1 000 rpm, the resulting ground stock having a fineness of ⁇ 45 ⁇ m. It was then moistened with denatured alcohol and the millbase into tablets with a Diameter of 2.54 cm and a thickness of 1 cm pressed (5.1 cm 3 ). After drying at 100 ° C, these tablets were fired for 12 hours at 1, 250 ° C in an electrically heated oven in air atmosphere. Subsequently, the fired tablets were ground and samples prepared for microscopic examinations and phase analyzes by means of X-ray powder diffractometry.
- FIG. 2 shows each other X-ray diffractograms of the compositions 1, 2, 5 and 6-2.
- all reflexes can be assigned to a singular ESS mineral phase or ESS monophase, while compositions 5 and 6-2 clearly have at least one second crystalline mineral phase.
- compositions 5 and 6-2 Since the X-ray diffractometer images were carried out with the same parameters, it can be clearly seen from the peak height and peak configuration that in the case of compositions 5 and 6-2 there is multiphase, while the images of compositions 1 and 2 clearly show the single-phase nature.
- Figures 3 to 6 show the light micrographs of compositions 1, 2, 5 and 6-2.
- the photographs in Figs. 3 and 4 show only the Spinellmonophase "S" of the compositions 1 and 2 of the inventive Sinterspinell Suite of the ternary system MgO, Fe 2 0 3, Al 2 0 3.
- the photographs in Figs. 5 and 6 show as Main phase the spinel phase "ST and to a lesser extent the spinel phase” S2 ". A single monophase is therefore not available.
- FIGS. 7a and 7b The oxidation resistance of ESS according to the invention is shown in FIGS. 7a and 7b.
- FIG. 7 a shows the X-ray diffractogram after the preparation of an ESS with the composition 1.
- FIG. Fig. 7b shows the X-ray diffractogram after treatment of the ESS at 1, 250 ° C and 12 hours in an air atmosphere in an electrically heated oven. It can be seen that the original spinel structure has been preserved despite the influence of temperature and the presence of oxygen. A new formation of mineral phases could not be determined by X-ray powder diffractometry.
- FIG. 8 a For comparison, a hercynite sample according to DE 44 03 869 A1 was melted and an X-ray diffractogram was created (FIG. 8 a). Thereafter, the hercynite sample was also treated at 1250 ° C for 12 hours in an air atmosphere in the electrically heated furnace. The result is shown in FIG. 8b. It can be clearly seen that the original spinel structure was disturbed by the effect of temperature and oxidation of divalent iron (Fe 2+ ). The divalent cations necessary for the crystal lattice of the hercynite spinel are no longer available. The newly formed phases are hematite (Fe 2 0 3 ) and corundum (Al 2 0 3 ).
- the invention also relates to the production of basic refractory products, e.g. As basic refractory moldings and basic refractory materials.
- basic refractory products according to the invention have the following composition:
- binder in particular at least one organic binder such as lignosulfonate, dextrin, methyl cellulose.
- the physical and thermochemical properties include the following table:
- FIG. 1 0 shows the superiority of refractory products according to the invention with ESS compared with refractory products of the same composition with Pleonast.
- the left image in Figure 10 shows a sample made with 8.5% ESS. In each case the same particle size distribution is used. tions of the main component, namely fused magnesia and the spinel component has been used. In addition, the firing conditions were the same. After the ceramic firing, the samples were subjected to a standardized thermal shock resistance test at 1 .200 ° C. (30 cycles, 30 minutes each in accordance with DIN EN 993-1 1).
- the thermal shock resistance of the left ESS-containing undestructed sample is clearly visible, while the sample containing the right pleonast is cracked.
- the invention is particularly characterized by a granular Elastifi- Painters in the form of a broken granulate for refractory products, in particular for basic refractory products, mineral each consisting of a single-phase sintered Mischkristallspinell of the ternary system MgO-Fe 2 03-AI 2 03 from the composition range
- MgO 12 to 19.5, especially 15 to 17 wt .-%
- Fe 2 0 3 and Al 2 0 3 in the ratio range Fe 2 0 3 to Al 2 0 3 between 80 to 20 and 40 to 60 wt .-%. starting from a MgO content between 12 to 19.5 wt .-%, the respective mixed crystals each containing a Fe 2 0 3 - and Al 2 0 3 content in solid solution from the respective specified limited areas such that a Total composition to 100 wt .-% results.
- the elasticizer has: a grain density> 2.95, in particular> 2.99, preferably> 3.2 g / cm 3 , very preferably up to 3.7 g / cm 3 , measured 5 according to DIN EN 993-18 or less than 5, in particular less than 2 wt .-% secondary phases or
- Grain size distribution between 0 and 6, in particular between 0 and 4 mm, preferably with the following grain distributions, in each case with normal customary grain distributions, in particular Gaussian grain distributions, or with certain selected grain fractions or grain bands.
- the invention is also characterized in particular by a process for producing a monophasic sintered spinel, wherein
- MgO component at least one starting material from the following group is used: sintered magnesia, caustic magnesia, in particular with MgO contents above 96, preferably above 98 wt.
- Fe 2 0 3 component is used at least one starting material from the following group: hematite or magnetite, and in particular with Fe 2 0 3 contents above 90, preferably above 95 wt .-%
- AI 2 0 3 component is at least used a starting material from the following group: alpha and / or gamma alumina, in particular Al 2 0 3 content above 98, preferably above 99 wt .-%, preferably alpha and gamma alumina ,
- granules of recycled materials such as mill scale (Fe 2 0 3 ) or recycled magnesia (MgO) or magnesia spinel (Al 2 0 3 , MgO) can be used at least in part. It is furthermore advantageous if the components are comminuted and mixed with grinding energy in a grinding unit, preferably up to a fineness ⁇ 0.10, in particular ⁇ 0.05 mm, or the mixtures at temperatures between 1.200 and 1, 700, in particular be sintered between 1400 and 1600, preferably 1450 to 1550 ° C, in particular 5 to 7 hours, or the mixtures before sintering z. B.
- granulation or pressing in particular to granules z. B. with volumes between 10 and 20, in particular between 12 and 15 cm 3 , and bulk densities z. B. between 2.90 and 3.20, in particular between 3.0 and 3.1 g / cm 3 determined to DIN EN 993-18 are pressed preferably with pressing pressures between 40 MPa and 130 MPa, in particular between 60 and 100 MPa. Pressed moldings have z. B. Volumes between 1 .600 and 2,000 cm 3 .
- the invention also relates to a basic, ceramically fired or unburnt refractory product in the form of refractory shaped bodies, in particular pressed refractory shaped bodies or unshaped refractory masses, in particular consisting of:
- refractory binder 0 to 5, in particular 1 to 2 wt .-% of at least one known for refractory binder, in particular with at least one organic binder such as lignosulfonate, dextrin, methylcellulose, etc.
- the refractory products according to the invention containing the elastification granules are particularly suitable for use as the fire-side lining of industrial large-volume furnace units, which are operated with a neutral and / or oxidizing furnace atmosphere, in particular for the lining of cement rotary kilns.
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Abstract
Description
Claims
Priority Applications (9)
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RU2018144621A RU2018144621A (ru) | 2016-05-19 | 2017-03-23 | Огнеупорные шпинельные грануляты, подходящие для эластифицирования грубокерамических огнеупоров, способ их получения и их применение |
CN201780026634.6A CN109153614A (zh) | 2016-05-19 | 2017-03-23 | 适用于使粗陶瓷耐火制品弹性化的耐火尖晶石颗粒,其制备方法和其用途 |
JP2018560497A JP2019519453A (ja) | 2016-05-19 | 2017-03-23 | 粗セラミック耐火物を弾性化するのに適した耐火性スピネル粒状体、その製造方法および使用 |
US16/302,301 US20190185378A1 (en) | 2016-05-19 | 2017-03-23 | Spinel refractory granulates which are suitable for elasticizing heavy-clay refractory products, method for their production and use thereof |
KR1020187034240A KR20190009307A (ko) | 2016-05-19 | 2017-03-23 | 조대(coarse)-세라믹 내화성 산물의 탄성화에 적합한 내화성 스피넬 입자, 그의 제조 방법 및 용도 |
CA3024486A CA3024486A1 (en) | 2016-05-19 | 2017-03-23 | Spinel refractory granulates which are suitable for elasticizing heavy-clay refractory products, method for their production and use thereof |
EP17713279.2A EP3468938A1 (de) | 2016-05-19 | 2017-03-23 | Zur elastifizierung von grobkeramischen feuerfesterzeugnissen geeignete feuerfeste spinellgranulate, verfahren zu ihrer herstellung und ihre verwendung |
BR112018073646-5A BR112018073646A2 (pt) | 2016-05-19 | 2017-03-23 | granulados de espinélio refratários adequados para a elastificação de produtos refratários de cerâmica bruta, método para sua produção e seu uso |
MX2018014155A MX2018014155A (es) | 2016-05-19 | 2017-03-23 | Granulados de espinela refractarios adecuados para la elastificacion de productos refractarios de ceramica gruesa, procedimientos para su fabricacion y su uso. |
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DE102016109254.1A DE102016109254B4 (de) | 2016-05-19 | 2016-05-19 | Zur Elastifizierung von grobkeramischen Feuerfesterzeugnissen geeignetes feuerfestes Spinellgranulat, Verfahren zu dessen Herstellung, Feuerfesterzeugnis mit dem Spinellgranulat, Verwendung des Feuerfesterzeugnisses, Auskleidung eines Industrieofens mit dem Feuerfesterzeugnis |
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DE102017121452B9 (de) * | 2017-09-15 | 2024-04-04 | Refratechnik Holding Gmbh | Verfahren zur Herstellung einer porösen Sintermagnesia, Versatz zur Herstellung eines grobkeramischen feuerfesten Erzeugnisses mit einer Körnung aus der Sintermagnesia, Verwendung des Versatzes zur Herstellung des Erzeugnisses sowie Verfahren zur Herstellung des Erzeugnisses |
CN112745130A (zh) * | 2020-12-30 | 2021-05-04 | 福建省佳美集团公司 | 一种耐火陶瓷的配方及陶瓷产品的制备方法 |
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DE202013012201U1 (de) * | 2013-12-10 | 2015-08-03 | Refratechnik Holding Gmbh | Grobkeramisches feuerfestes Erzeugnis |
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2016
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2017
- 2017-03-23 KR KR1020187034240A patent/KR20190009307A/ko not_active Application Discontinuation
- 2017-03-23 BR BR112018073646-5A patent/BR112018073646A2/pt not_active Application Discontinuation
- 2017-03-23 CA CA3024486A patent/CA3024486A1/en not_active Abandoned
- 2017-03-23 US US16/302,301 patent/US20190185378A1/en not_active Abandoned
- 2017-03-23 MX MX2018014155A patent/MX2018014155A/es unknown
- 2017-03-23 JP JP2018560497A patent/JP2019519453A/ja active Pending
- 2017-03-23 CN CN201780026634.6A patent/CN109153614A/zh active Pending
- 2017-03-23 RU RU2018144621A patent/RU2018144621A/ru not_active Application Discontinuation
- 2017-03-23 WO PCT/EP2017/056998 patent/WO2017198377A1/de unknown
- 2017-03-23 EP EP17713279.2A patent/EP3468938A1/de not_active Withdrawn
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EP3468938A1 (de) | 2019-04-17 |
RU2018144621A3 (de) | 2020-06-19 |
RU2018144621A (ru) | 2020-06-19 |
US20190185378A1 (en) | 2019-06-20 |
CA3024486A1 (en) | 2017-11-23 |
DE102016109254B4 (de) | 2018-08-09 |
JP2019519453A (ja) | 2019-07-11 |
BR112018073646A2 (pt) | 2019-02-19 |
DE102016109254A1 (de) | 2017-11-23 |
CN109153614A (zh) | 2019-01-04 |
MX2018014155A (es) | 2019-08-16 |
KR20190009307A (ko) | 2019-01-28 |
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