EP3927673A2 - Refractory compound and binder therefor, method for the production and use thereof - Google Patents
Refractory compound and binder therefor, method for the production and use thereofInfo
- Publication number
- EP3927673A2 EP3927673A2 EP20709506.8A EP20709506A EP3927673A2 EP 3927673 A2 EP3927673 A2 EP 3927673A2 EP 20709506 A EP20709506 A EP 20709506A EP 3927673 A2 EP3927673 A2 EP 3927673A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- refractory
- microscale
- binder
- bonds
- 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.)
- Pending
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
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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
- C04B35/101—Refractories from grain sized mixtures
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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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- C—CHEMISTRY; METALLURGY
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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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/624—Sol-gel processing
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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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- 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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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- 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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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- 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
- C04B35/62665—Flame, plasma or melting treatment
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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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- 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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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- 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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- C04B2235/00—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
- C04B2235/3217—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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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- 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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- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5212—Organic
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
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- C04B2235/5409—Particle size related information expressed by specific surface values
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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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
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- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
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%
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Products (AREA)
- Mold Materials And Core Materials (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102019001214.3A DE102019001214A1 (en) | 2019-02-20 | 2019-02-20 | Refractory compounds and binders therefor, processes for their production and use |
DE202019003290 | 2019-08-07 | ||
PCT/EP2020/054551 WO2020169772A2 (en) | 2019-02-20 | 2020-02-20 | Refractory compound and binder therefor, method for the production and use thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3927673A2 true EP3927673A2 (en) | 2021-12-29 |
Family
ID=69770864
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20709506.8A Pending EP3927673A2 (en) | 2019-02-20 | 2020-02-20 | Refractory compound and binder therefor, method for the production and use thereof |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP3927673A2 (en) |
BR (1) | BR112021015523A2 (en) |
MX (1) | MX2021009952A (en) |
WO (1) | WO2020169772A2 (en) |
ZA (1) | ZA202106305B (en) |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4093470A (en) | 1976-10-20 | 1978-06-06 | Combustion Engineering, Inc. | Alumina refractories |
DE3002763A1 (en) * | 1980-01-26 | 1981-07-30 | Dörentruper Sand-und Thonwerke GmbH, 4926 Dörentrup | Refractory mass based on dry quartz or silica grains - plus binder which decomposes when heated to form only silica |
DE4109916A1 (en) | 1990-03-26 | 1991-10-02 | Norton Co | Thermally conductive metal-contg. refractory compsn. - esp. mortar for bending shields and blocks to boiler tubes with high thermal conductivity |
US5494267A (en) * | 1994-07-26 | 1996-02-27 | Magneco/Metrel, Inc. | Pumpable casting composition and method of use |
EP0842910A3 (en) | 1996-11-14 | 1998-12-16 | Bayerisches Zentrum für Angewandte Energieforschung e.V. ZAE Bayern | Binder based on waterglass solution, process for its preparation and its utilisation |
US6268018B1 (en) * | 1999-02-09 | 2001-07-31 | Harbison-Walker Refractories Company | Method of applying a non-slumping pumpable castable high purity silica composition |
US8505335B2 (en) * | 2007-06-19 | 2013-08-13 | Magneco/Metrel, Inc. | Refractoy composition for glass melting furnaces |
DE102014019351A1 (en) | 2014-12-22 | 2016-06-23 | Refratechnik Holding Gmbh | Refractory products and their use |
-
2020
- 2020-02-20 BR BR112021015523-6A patent/BR112021015523A2/en unknown
- 2020-02-20 MX MX2021009952A patent/MX2021009952A/en unknown
- 2020-02-20 EP EP20709506.8A patent/EP3927673A2/en active Pending
- 2020-02-20 WO PCT/EP2020/054551 patent/WO2020169772A2/en unknown
-
2021
- 2021-08-30 ZA ZA2021/06305A patent/ZA202106305B/en unknown
Also Published As
Publication number | Publication date |
---|---|
BR112021015523A2 (en) | 2021-10-05 |
WO2020169772A3 (en) | 2020-11-12 |
WO2020169772A2 (en) | 2020-08-27 |
MX2021009952A (en) | 2021-10-13 |
ZA202106305B (en) | 2023-12-20 |
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