WO2020169772A2 - Masse réfractaire et agent liant pour celle-ci, procédé pour sa production ainsi qu'utilisation - Google Patents

Masse réfractaire et agent liant pour celle-ci, procédé pour sa production ainsi qu'utilisation Download PDF

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Publication number
WO2020169772A2
WO2020169772A2 PCT/EP2020/054551 EP2020054551W WO2020169772A2 WO 2020169772 A2 WO2020169772 A2 WO 2020169772A2 EP 2020054551 W EP2020054551 W EP 2020054551W WO 2020169772 A2 WO2020169772 A2 WO 2020169772A2
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WO
WIPO (PCT)
Prior art keywords
weight
refractory
microscale
binder
bonds
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PCT/EP2020/054551
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German (de)
English (en)
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WO2020169772A3 (fr
Inventor
Manfred Knoll
Natalie Fröse
Original Assignee
Intocast Ag
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
Priority claimed from DE102019001214.3A external-priority patent/DE102019001214A1/de
Application filed by Intocast Ag filed Critical Intocast Ag
Priority to EP20709506.8A priority Critical patent/EP3927673A2/fr
Priority to MX2021009952A priority patent/MX2021009952A/es
Priority to BR112021015523-6A priority patent/BR112021015523A2/pt
Publication of WO2020169772A2 publication Critical patent/WO2020169772A2/fr
Publication of WO2020169772A3 publication Critical patent/WO2020169772A3/fr
Priority to ZA2021/06305A priority patent/ZA202106305B/en

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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C—CHEMISTRY; METALLURGY
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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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    • C04B30/00—Compositions for artificial stone, not containing binders
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
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    • C04B35/624—Sol-gel processing
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    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/6263—Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
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    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
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    • C04B35/62605—Treating the starting powders individually or as mixtures
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    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/6303—Inorganic additives
    • C04B35/6316—Binders based on silicon compounds
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    • C04B2111/00431—Refractory materials
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
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    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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Definitions

  • the invention relates to a refractory mass, a binding agent for it, a method for fusing a refractory mass and a bonding system and a use of microscale amorphous silicon dioxide according to the preamble of the independent claims.
  • High alumina cements are considered to be the most commonly used conventional binders in refractory unshaped products.
  • the bond is activated by the calcium aluminates contained in these cements by adding water.
  • silica sol solutions have increasingly been used as binders.
  • Silica sol solutions are aqueous, colloidal dispersions made from nanoscale amorphous silicon dioxide particles.
  • the refractory products bound with it are characterized by good alkali and acid resistance compared to cement-bound compounds.
  • the silica sol-bound materials can be heated up quickly due to the lack of hydrate phases, which leads to significant energy and cost savings.
  • microscale amorphous silicon dioxide can be mixed as a dry powder with the other components of the mass, so that a silica gel is formed when water is added to the total mass.
  • the binding systems of DE 27 39 767 A1, EP 0 842 910 A2 and DE 30 02 763 A1 are based on clays with the addition of a phosphate acid / hydrochloric acid, and on what serglas / liquid silica sol.
  • the invention is based on the object of creating an improved refractory mass with an improved bonding system, a method for the respective production and a use of microscale amorphous silicon dioxide according to the preamble of the independent claims.
  • the invention proposes for the first time the use of small amounts (in particular ⁇ 1% by weight or 0.1-1% by weight) of a microscale amorphous silicon dioxide as the sole binder for bond formation in unshaped refractory materials.
  • microscale Si0 2 system for bond formation instead of water-containing cement phases.
  • This can be done, for example, by using silica sol solutions.
  • the mass to be bound is mixed with the silica sol solution, processed and allowed to harden.
  • microscale amorphous Si0 2 can be mixed as a dry powder with the other constituents of the mass, so that a silica gel is formed in the mass when the total mass is mixed with water.
  • the advantage of this procedure is that there is no silica sol solution, the reactivity of which is Storage processes and storage conditions is influenced, must be provided separately.
  • a binding system is generated by dispersing microscale amorphous silicon oxide under the action of water, which can be used for binding formation in refractory, unshaped products.
  • the microscale SiO 2 used for the formation of bonds is a product that can be obtained as an amorphous precipitate via a precipitation reaction and has a purity of approx. 90-99.9% by weight (in the dried state), a mean grain size in the micrometer range ( 1 -50 miti, in particular 1 -10 miti, 1 -20 miti, 1 -30 miti, or 1 -40 miti) and a specific surface area of approx. 50-350 m 2 / g, in particular 100-350 m 2 / g , 200-350 m 2 / g, or 250-300 m 2 / g.
  • silica gels contain (H 2 Si0 5 ) x units that are held together by van der Waals bonds and hydrogen bonds and between which particles of different chemical composition and different grain sizes can be included. When the gel dries, a Si0 2 framework remains which continues to surround the introduced grains.
  • the method according to the invention relates to the production of a Si0 2 binding system by using a dry Si0 2 binder, which contains ⁇ 1% by weight, in particular 0.1-1% by weight, of the total mass with the solid constituents to be bound mixed and, after adding about 1-30% by weight, in particular 1-10% by weight, 10-30% by weight, 15-30% by weight or 20-30% by weight of water, used to form bonds becomes.
  • the speed of hydration of the Si0 2 , the coagulation to the silica gel and the subsequent dehydration of the gel depends on the temperature, pH, material composition and material thickness.
  • the microscale Si0 2 -based binding system has a significantly lower reaction dependency with regard to the temperature and the chemical composition than cement-bound binding systems.
  • the bond formation can therefore be used for the production of a variety of refractory masses different raw material composition as spray, vibration, soap flow or casting compound.
  • the refractory materials produced according to the invention after they have been cast into cylinders and dried at 110 ° C., alternatively 100-150 ° C., 105-125 ° C., usually have a compressive strength of> 15 MPa. Due to the lower tendency of silica gels to spallate compared to calcium aluminate hydrate phases, the products made with microscale SiO 2 binders offer the advantage of being able to be heated up more quickly without damage.
  • Example 1 for refractory masses (given in% by weight):
  • MgO very fine ⁇ 1%, especially 0.1% to 1%
  • Example 2 for refractory masses (given in% by weight):
  • MgO very fine ⁇ 1%, especially 0.1% to 1%

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Ceramic Products (AREA)
  • Mold Materials And Core Materials (AREA)

Abstract

L'invention concerne une masse réfractaire non moulée, en particulier une masse à couler, injecter et/ou autocoulable, comprenant un système de liaison se formant à l'ajout d'eau et un agent liant SiO2- sec amorphe à échelle micrométrique, comme unique agent liant, lequel est mélangé dans une proportion ≤ 1% en poids de la masse totale avec les composants solides à lier et forme le système de liaison après l'ajout de 1-30% en poids d'eau. L'invention concerne en outre un procédé pour la production de masses réfractaires et une utilisation de dioxyde de silicium amorphe microcristallin dans la production de masses réfractaires.
PCT/EP2020/054551 2019-02-20 2020-02-20 Masse réfractaire et agent liant pour celle-ci, procédé pour sa production ainsi qu'utilisation WO2020169772A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP20709506.8A EP3927673A2 (fr) 2019-02-20 2020-02-20 Masse réfractaire et agent liant pour celle-ci, procédé pour sa production ainsi qu'utilisation
MX2021009952A MX2021009952A (es) 2019-02-20 2020-02-20 Mezcla refractaria y aglutinante para la misma, metodo para su produccion y su uso.
BR112021015523-6A BR112021015523A2 (pt) 2019-02-20 2020-02-20 Massas refratárias e agente de ligação para as mesmas, processo para sua produção e utilização
ZA2021/06305A ZA202106305B (en) 2019-02-20 2021-08-30 Refractory compound and binder therefor, method for the production and use thereof

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102019001214.3A DE102019001214A1 (de) 2019-02-20 2019-02-20 Feuerfestmasse und Bindemittel dafür, Verfahren zur deren Herstellung sowie Verwendung
DE102019001214.3 2019-02-20
DE202019003290 2019-08-07
DE202019003290.8 2019-08-07

Publications (2)

Publication Number Publication Date
WO2020169772A2 true WO2020169772A2 (fr) 2020-08-27
WO2020169772A3 WO2020169772A3 (fr) 2020-11-12

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PCT/EP2020/054551 WO2020169772A2 (fr) 2019-02-20 2020-02-20 Masse réfractaire et agent liant pour celle-ci, procédé pour sa production ainsi qu'utilisation

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Country Link
EP (1) EP3927673A2 (fr)
BR (1) BR112021015523A2 (fr)
MX (1) MX2021009952A (fr)
WO (1) WO2020169772A2 (fr)
ZA (1) ZA202106305B (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2739767A1 (de) 1976-10-20 1978-04-27 Combustion Eng Feuerfestes material auf der basis aluminiumoxid und verdampftes siliciumdioxid
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DE2739767A1 (de) 1976-10-20 1978-04-27 Combustion Eng Feuerfestes material auf der basis aluminiumoxid und verdampftes siliciumdioxid
DE3002763A1 (de) 1980-01-26 1981-07-30 Dörentruper Sand-und Thonwerke GmbH, 4926 Dörentrup Feuerfestmasse
DE4109916A1 (de) 1990-03-26 1991-10-02 Norton Co Zusammensetzung, insbesondere verwendbar als feuerfester moertel
EP0842910A2 (fr) 1996-11-14 1998-05-20 Bayerisches Zentrum für Angewandte Energieforschung e.V. ZAE Bayern Liant à base d'une solution de verre soluble, procédé pour sa préparation et son utilisation
DE102014019351A1 (de) 2014-12-22 2016-06-23 Refratechnik Holding Gmbh Feuerfeste Erzeugnisse und ihre Verwendung

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