EP2539295A2 - Pièce moulée réfractaire isolante à résistance thermique élevée - Google Patents

Pièce moulée réfractaire isolante à résistance thermique élevée

Info

Publication number
EP2539295A2
EP2539295A2 EP11709864A EP11709864A EP2539295A2 EP 2539295 A2 EP2539295 A2 EP 2539295A2 EP 11709864 A EP11709864 A EP 11709864A EP 11709864 A EP11709864 A EP 11709864A EP 2539295 A2 EP2539295 A2 EP 2539295A2
Authority
EP
European Patent Office
Prior art keywords
fibers
weight
silica
binder
cenospheres
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP11709864A
Other languages
German (de)
English (en)
Inventor
Rainer Angenendt
Peer Genth
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tdh - Technischer Dammstoffhandel GmbH
Original Assignee
Tdh - Technischer Dammstoffhandel GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tdh - Technischer Dammstoffhandel GmbH filed Critical Tdh - Technischer Dammstoffhandel GmbH
Publication of EP2539295A2 publication Critical patent/EP2539295A2/fr
Ceased legal-status Critical Current

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    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
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    • C04B28/003—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hybrid binders other than those of the polycarboxylate type
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    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention relates to a heat-insulating refractory high-temperature resistant molded part containing a plurality of lightweight fillers, a binder and fibers and / or wollastonite, for applications up to about 1600 ° C.
  • lightweight fillers is to be understood here as high-melting mineral granules of low density, for example fly ash, expanded volcanic rocks, expanded perlite, etc.
  • Refractory bricks are formed refractory products with a total porosity> 45% and an application temperature of at least 800 ° C.
  • ASTM C 155-70 and DIN EN 1094 define the temperature at which the shrinkage of the material after 24 h or 12 h is not more than 2% and a maximum density.
  • silicate bricks To divide lightweight refractory bricks, silicate bricks, zirconia and corundum light bricks. The greatest importance and spread comes to the aluminum silicate light bricks (chamotte and mullite bricks).
  • alumina carrier For the production of raw materials based on A1 2 0 3 , Si0 2 and possibly CaO are used.
  • alumina carrier are raw materials such as clay, kaolin, chamotte,
  • Sillimanite, andalusite, kyanite and mullite and alumina, alumina hydrate and corundum used.
  • fine-grained raw materials In addition to the fine-grained raw materials, coarse-grained, porous raw materials such as lightweight chamotte and hollow spheres made from corundum and mullite are also used.
  • Known refractory bricks have a bulk density of 0.5 to 1.4 g / cm 3 , a
  • German Offenlegungsschrift DE 10 2007 012 489 A1 describes exclusively insulating and exothermic feeders from the foundry industry.
  • Chapter 1 is a term from the foundry industry and refers to geometric sprues on castings, in the form of the voids volume deficit is to be placed during the casting solidification and which are removed in the cleaning process of the castings again.
  • the feeders themselves are destroyed in this process (disposable parts).
  • a feeder has the task of avoiding the formation of voids (cavities) in a casting, and has other different tasks in a casting mold:
  • the exothermic feeders described in DE 10 2007 012 489 A1 contain thermally similar mixtures which are very dangerous and have led to extreme fires in some factories.
  • the thermite reaction is a redox reaction in which aluminum is used as a reducing agent, e.g. Iron (III) oxide to reduce iron.
  • the mixture is called thermite:
  • the reaction products are alumina and elemental iron.
  • the reaction is very exothermic, ie under strong heat.
  • the ignition medium used is barium peroxide with magnesium.
  • Thermitgemische are not explosives and can be brought to implementation (inflammation) only by a very large heat input (activation energy).
  • the burning process is a strongly exothermic reaction (up to 3000 ° C). Since burning thermite does not require external oxygen, the reaction can not be stifled and in any environment - even under sand or water - be ignited and continue to burn. Extinguishing tests with water and moisture lead to a further redox reaction, in which the water is reduced by the less noble metals and thus metal oxide and hydrogen are formed:
  • base material mixed with binder with a certain firing pressure and possibly defined working temperature is introduced into a core mold (the "core box"). After hardening or precuring of the casting core thus produced, it is installed in the casting mold.
  • core box a core mold
  • so-called cold box or hot box core shooting machines are used.
  • the blends in the present patent application contain significantly more water. In the recipe, the water content is at least 10 wt% and larger. The blends in the present patent application therefore correspond to their consistency ramming masses or plastic masses.
  • the binders listed in DE 10 2007 012 489 A1 are exclusive
  • Thermoplastics also known as plastomers, are plastics that can be deformed in a specific temperature range (thermo-plastic). This process is reversible, that is, it can be repeated as often as desired by cooling and reheating to the molten state, as long as not using the so-called thermal decomposition of the material by overheating.
  • Thermoplastics are mainly processed by injection molding, which is similar to the core shooting method described in DE 10 2007 012 489 AI.
  • the thermoplastics include z. Acrylonitrile-butadiene-styrene (ABS), polyamides (PA), polylactate (PLA), polymethylmethacrylate (PMMA), polycarbonate (PC),
  • PET Polyethylene terephthalate
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • PEEK polyetheretherketone
  • PVC polyvinyl chloride
  • thermoplastic binders In no way are the properties of thermoplastic binders to be compared with the hybrid binders described in the present patent application which must ensure strength over a wide temperature range.
  • the invention has for its object to provide extremely stable moldings of the type mentioned, which have a density of less than 1.0 g / cm 3 , to about a maximum of 1500 ° C virtually no shrinkage, namely less than 1.0%, and show up to this temperature no external or internal cracks and no crumbling and for continuous temperatures up to about 1600 ° C are suitable and the one clearly show higher cold compressive strength than refractory bricks comparable gross density and comparable thermal conductivity show.
  • the geometry of the molded parts is basically no limit. Bricks, pipes, hollow bodies and other molded parts can be produced.
  • aqueous mass which are prepared by known shaping processes, subsequent drying and thermal treatment in various stages from 950 to about 1450 ° C.
  • the following molding methods are suitable:
  • the kaolin present in the plastic starting material is converted into spinel and quartz, which then serves as a binder for the not yet melted at this temperature volcanic rocks.
  • the surface of the cenospheres can be adjusted to the requirements in a targeted manner by adding or exchanging minerals and melts in the flux. With approximately the same densities and thermal properties can be adjusted to the requirements in a targeted manner by adding or exchanging minerals and melts in the flux. With approximately the same densities and thermal properties can be adjusted to the requirements in a targeted manner by adding or exchanging minerals and melts in the flux. With approximately the same densities and thermal properties can be adjusted to the requirements in a targeted manner by adding or exchanging minerals and melts in the flux. With approximately the same densities and thermal properties can
  • lightweight flameproof can be used up to 1600 ° C moldings with adapted to the intended use surfaces of the cenospheres.
  • the content of fibers and / or wollastonite serves to cohesion of the mass in the wet state.
  • the hybrid binder provides for the cohesion after drying at temperatures up to about 200 ° C due to the organic component and at higher temperatures by the sintering of the silica particles.
  • the kaolin used and the silica sol are also a binder, which at elevated
  • the light fillers namely the microcellularly expanded volcanic rocks and the cenospheres provide the necessary volume and a relatively low density compared to the prior art.
  • the microcellularly inflated volcanic rocks soften at temperatures above about 1000 ° C and higher and then serve as a flux and binder between the
  • microcellular expanded volcanic stones are surface treated to protect against water attack in the plastic masses and mortars, thereby rendering the masses shelf stable.
  • inflated cellular volcanic rock in the form of nonporous hollow granules is used as light filler.
  • porous hollow granules on the other hand, the bulk density would increase, more glue and more minerals would be required, the masses would become duller and thus would be worse to process and the porosity of the end product would increase significantly.
  • the main constituent of the composition according to the invention are fly ash cenospheres, which in particular have a proportion of from 20 to 45% by weight.
  • Fly ash is the solid, disperse (particulate, particulate, dusty) residue of burns, which is due to its high dispersity (fineness) discharged with the flue gases. Fly ash is produced in large quantities in
  • the particle size ranges from about 1 ⁇ to 1 mm.
  • Particle shapes include both smooth, massive spheres and hollow spheres (so-called cenospheres), platelets, fibers and agglomerates.
  • the density is 2.2 to 2.4 kg / dm 3
  • the bulk density is between 0.9 to 1.1 kg / dm 3 .
  • the composition of the fly ash strongly depends on the fuel (lignite or
  • Hard coal and extends from residual carbon and minerals (quartz) to toxic substances such as heavy metals (arsenic to zinc) and dioxins.
  • the fly ash also acts as a carrier of adsorbed pollutants. While pure, uniform, consistent fuels such as hard coal provide a good usable fly ash, the brown coal fly ash (BFA) is composed of many different substances. Due to their chemical and physical properties, such as the pozzolanic reactivity, the spherical grain shape and the grain distribution, hard coal fly ash (SFA) in particular is a high - quality secondary raw material and is found in the
  • fly ash is used in the building materials industry according to DIN EN 450 as an additive in cement and concrete. Furthermore, the fly ash can be used for the production of bricks made of sand-lime brick or aerated concrete. In road and earthworks, the fly ash is used together with Gesteinskömung as a building material for unbound base courses.
  • Kaolin / Silica Kieselsol Kaolin also referred to as china clay or aluminum silicate, is a fine, iron-free, white rock containing as its main constituent kaolinite, a weathering product of feldspar.
  • the kaolin used as a film covers the high-melting light filler and forms a solid structure even at about 900 ° C.
  • Shrinkage is affected by the ratio of kaolin / silica / silica sol and their distribution.
  • Another advantage of the used mixture of kaolin silica silica sol is that the mass after hardening is hard and mechanically stable.
  • Binders is used with a binding effect in different temperature ranges.
  • the innovation of the product according to the invention is, in particular, that suitable, complementary binder systems are used, for. B. the
  • Hybrid binder which already has the support structures made of fibers in the
  • Volcanic rocks as a flux for the additional minerals and as a fixation for the cenospheres. Due to the cavities formed by the melting, stresses can be buffered by increasing the temperature and expanding within the mass.
  • a key customer benefit when using the products according to the invention is that in addition to the desired goal of efficient high-temperature insulation a Significant cost savings in the area of opportunity costs for customers can be realized. The reduction of these costs is achieved primarily by improving the energy balance and also the life cycle assessment by reducing emissions for the customer.
  • Perlite (English: perlite) referred to in geosciences an altered (chemically and physically transformed) volcanic glass (obsidian) and is thus one of the rocks.
  • the so-called pearlitic structure is formed here by approximately pea-sized glass beads.
  • Perlite contains up to 2% water and has a density of about 900 to 1000 kg / m 3 (bulk density of crude perlite).
  • microcellularly-expanded volcanic rocks are suitable for the purposes of the invention, produced according to new environmentally friendly and energy-saving methods, and achieve properties and technical values that expand from older, porous ones
  • Microcellular, expanded volcanic rock is a filler from the group of aluminum silicates and consists of spherical ("honeycomb"), rod-shaped and flaky particles resulting in high packing densities and higher bond strengths than conventional hollow microspheres due to mechanical and cohesive bonding forces.
  • Targeted surface coatings enable an advantageous bond with the inorganic or organic matrix. This results in less shrinkage and better technical properties.
  • Commercially available is blown impregnated perlite z. B. under the trade name NOBLITE® (product of the company NOBLITE, Route de Claye, F-77181 LE PIN, France) and Technoperl® (product of Europerl Germany, D-94032 Passau, Nibelebenplatz 4).
  • ceramic and / or mineral high-melting fibers and / or organic high-melting fibers, for example carbon fibers are used.
  • Wollastonite is also possible.
  • Ceramic fibers or ceramic fibers are fibers
  • inorganic, non-metallic material inorganic, non-metallic material.
  • ceramic polycrystalline inorganic materials
  • precursors produced by pyrolysis amorphous fibers, which are referred to by their properties as ceramic fibers.
  • amorphous glass fibers which are not counted among the ceramic fibers, is best made possible by the manufacturing process (glass fibers from glass melt, amorphous ceramic fibers from polymeric precursors by pyrolysis).
  • the ceramic fibers are classified into oxidic and non-oxidic.
  • oxidic ceramic fibers fibers based on alumina and silica in different proportions and in part even with additional boron oxide or zirconium oxide are known.
  • Mixed oxide fibers of 85% A1 2 0 3 and 15% Si0 2 are also referred to as mullite fibers. All of these fibers are polycrystalline.
  • Non-oxide, industrially produced fibers have various types of silicon carbide fibers known.
  • Starting polymers are almost exclusively so-called poly-carbosilanes. These are polymers of hydrocarbons in which individual carbon atoms have been replaced by silicon atoms or silanes in which individual silicon atoms have been replaced by carbon atoms. Additives crosslink the polymers in a hardening process so that they can be used after the P2011 / 000872
  • Spinning process in the pyrolysis not simply evaporate, but - as in the production of carbon fibers - are converted into an amorphous, usually non-stoichiometric, still free carbon-containing SiC ceramic fiber.
  • an organic-inorganic hybrid binder which is obtainable under the trade name COL.9 from BASF. It contains 50 to 100 nm composite particles containing amorphous silica particles 5 and a polymer 6 based on n-butyl acrylate and methyl methacrylate (see Figure 1). The particles are dispersed in water. Due to the stickiness of the particles due to the polymer content is obtained an excellent binder for low temperatures, up to about 200 ° C. At elevated temperatures, the polymer fraction decomposes and the silica particles remain and thus preserve the structure, wherein the silica particles also forms a solid framework at a correspondingly high temperature. Shrinkage therefore does not occur at low or elevated
  • the binder has a solids content of about 35 to 40% by weight.
  • the silicate content, based on the solids content, is 30 to 50 wt .-%.
  • a surface-treated silica is used.
  • Silica is an intimate mixture of finely divided silica and kaolinite.
  • the Neuburg Siliceous Earth is known, which is preferably used according to the invention.
  • the silica is treated with a silane so that the individual particles have a functional hydrophilic surface.
  • Such an activated silica is available under the trade name "AKTISIL EM” from Hoffmann Mineral GmbH, Neuburg (Danube) Here, the silica is treated with 3-epoxypropyloxipropyltrimethoxysilane.
  • This so-called activated silica can be used in powder form the use of a mixture of silica sol and kaolin / kaolinite. Production examples and example formulations for the plastic mass used to produce the molded parts
  • step 1 mix all the liquid components of the recipe; then the components are weighed separately according to the recipe. step 1
  • Mixer to be used e.g. beba compulsory mixer
  • the premix now has a creamy consistency and may no longer contain lumps. If there are any lumps left, rasp them by hand, mix again with the same setting until there are no more lumps.
  • the mass must correspond to a loose bed to a pourable mortar.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)

Abstract

L'invention concerne une pièce moulée réfractaire isolante à résistance thermique élevée qui convient à des températures d'utilisation continue comprises entre 1200 et 1600 °C et qui contient plusieurs matières de charge légères, un produit réactionnel du durcissement thermique d'un liant et des fibres et/ou de la wollastonite. La pièce moulée selon l'invention est caractérisée en ce qu'elle contient des cénosphères provenant de cendres volantes et de roches volcaniques expansées à cellules fermées en tant que matières de charge légères, en ce qu'elle contient des fondants et en ce qu'elle contient du dioxyde de silicium en tant que produit réactionnel du durcissement thermique du liant.
EP11709864A 2010-02-24 2011-02-23 Pièce moulée réfractaire isolante à résistance thermique élevée Ceased EP2539295A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201010009148 DE102010009148B4 (de) 2010-02-24 2010-02-24 Wärmedämmendes feuerfestes hochtemperaturbeständiges Formteil
PCT/EP2011/000872 WO2011104008A2 (fr) 2010-02-24 2011-02-23 Pièce moulée réfractaire isolante à résistance thermique élevée

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DE102010048175B4 (de) 2010-10-13 2016-07-21 Werner Bloem Aktives schadstoffreduzierendes Formteil
DE102010048174B4 (de) 2010-10-13 2015-04-02 TDH - GmbH Technischer Dämmstoffhandel Intumeszentes wärmedämmendes feuerfestes Formteil und Verfahren zu dessen Herstellung
WO2018033219A1 (fr) * 2016-08-19 2018-02-22 Wacker Chemie Ag Corps moulé poreux sous la forme d'une couche de plâtre isolant ou d'une plaque isolante
CN106495738B (zh) * 2016-10-25 2019-04-16 中电声韵声学工程技术(北京)有限公司 一种陶瓷吸声材料及其制备方法与用途
CN111732424A (zh) * 2020-07-14 2020-10-02 黑龙江火山岩科技有限公司 火山岩低膨胀陶瓷坯料及火山岩低膨胀陶瓷的制备方法
CN111995419A (zh) * 2020-09-02 2020-11-27 巩义市益鑫耐火材料厂 一种铁水预处理用环保型强化复合脱磷包砖及其制备方法
CN113511904B (zh) * 2021-04-22 2022-06-14 武汉科技大学 一种轻量莫来石质耐火材料及其制备方法
CN113563092B (zh) * 2021-07-29 2023-12-22 阿尔赛(苏州)无机材料有限公司 一种空心球陶瓷纤维砖及其制备方法
CN116553921B (zh) * 2023-02-27 2024-06-25 河南三元光电科技有限公司 一种耐高温隔热复合材料及其制备方法

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WO2011104008A2 (fr) 2011-09-01
DE102010009148B4 (de) 2013-10-10
DE102010009148A1 (de) 2011-08-25
WO2011104008A3 (fr) 2011-10-20

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