GB2216116A - Refractory compositions containing magnesium oxide - Google Patents

Refractory compositions containing magnesium oxide Download PDF

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Publication number
GB2216116A
GB2216116A GB8904513A GB8904513A GB2216116A GB 2216116 A GB2216116 A GB 2216116A GB 8904513 A GB8904513 A GB 8904513A GB 8904513 A GB8904513 A GB 8904513A GB 2216116 A GB2216116 A GB 2216116A
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Prior art keywords
composition
bonding agent
refractory
agent system
respect
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Granted
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GB8904513A
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GB2216116B (en
GB8904513D0 (en
Inventor
Hartmut Hlawatschek
Juergen Zimmer
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Didier Werke AG
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Didier Werke AG
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Publication of GB8904513D0 publication Critical patent/GB8904513D0/en
Publication of GB2216116A publication Critical patent/GB2216116A/en
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Publication of GB2216116B publication Critical patent/GB2216116B/en
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing 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
    • C04B35/632Organic additives
    • C04B35/634Polymers
    • C04B35/63448Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63472Condensation polymers of aldehydes or ketones
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/013Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics containing carbon
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/03Shaped 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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
    • C04B35/04Shaped 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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
    • C04B35/043Refractories from grain sized mixtures
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing 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
    • C04B35/632Organic additives
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing 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
    • C04B35/632Organic additives
    • C04B35/634Polymers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66Monolithic refractories or refractory mortars, including those whether or not containing clay
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422Carbon

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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)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Products (AREA)

Description

2216116 REFRACTORY COMPOSITIONS CONTAINING MAGNESIUM OXIDE The invention
relates to refractory compositions containing magnesium oxide, particularly ramming compositions, and is concerned with that type of composition which contains fired magnesite and/or fired dolomite as the principal refractory material and optionally further conventional components and 2 to 8 wt.%, with respect to the entire composition, of a temporary bonding agent system including a drying oil.
DE-C-2747636 discloses dolomite compositions which include linseed oil and a dry, inorganic, ground bonding agent and optionally paper dust and/or other carbon-containing materials as a bonding agent. DE-B2424936 further discloses tapping hole compositions which contain linseed oil and a heat-curable resin as the bonding agent. DE-B-2822653 discloses refractory compositions which contain a mixture of a phenolic resol resin and tall oil as the bonding agent. Furthermore, basic compositions are known, e.g. from DE-B-1274489 which contain pitch as the primary bonding agent component.
It is an object of the present invention to provide a magnesium oxidecontaining refractory composition which instead of pitch, tar or bitumen contains other more environmentally acceptable bonding agents, i.e. bonding agents which do not give off environmentally harmful gases, e.g. benzopyrene, when the compositions are subjected to heat. It is also desirable that the compositions should exhibit a good compressability.
It has now been found surprisingly that when using a bonding agent system which comprises not only one or more drying oils but also one or more unsaturated fatty 2 acids, a boron compound and a heat-curable resin,, refractory compositions can be produced which scarcely give off environmentally harmful substances when they are used, i.e. when subjected to high temperatures, but nevertheless have a high compressability.
- According to the present invention there is provided a refractory composition containing fired magnesite and/or fired dolomite as the principal refractory material and 2 to 8 wt.%, with respect to the weight of the entire composition, of a temporary bonding agent system comprising 30 to 50 wt.% of a drying oil, 30 to 50 wt.% of an unsaturated fatty acid, 5 to 20 wt.% of a boron compound and 5 to 20 wt.% of a heat- curable resin, the total of the components of the bonding agent system being 100 wt.%.
In a preferred embodiment the refractory composition additionally contains 1 to 8 wt.%, with respect to the entire composition, of graphite, soot and/or coke as a further component. The use of flakey graphite and/or petroleum coke is particularly preferred.
Fired magnesite and/or fired dolomite in the form of a suitable granulate is used as the principal refractory material in the refractory compositions in accordance with the invention. The grain size distribution of the granular material may be generally conventional, e.g. as follows:
0 to 0.6 mm 40% 0.6 to 1.5 mm 15% 1.5 to 6 mm 45% The maximum grain size can be limited to a value of 3 mm or 4 mm in which case the amount present of the 3 largest size is then in respect of the range 1.5 to 3mm or 1.5 to 4 mm, respectively.
As described above, the refractory compositions in accordance with the invention can additionally contain graphite, soot and/or coke in finely divided form, flakey graphite and/or coke being particularly preferred. These additives are preferably used if particular refractory characteristics of the composition are desirable, e. g. a better slag resistance or slag infiltration resistance.
As stated above, a bonding agent system which comprises a total of four components is used in the refractory composition in accordance with the invention.
The first component, which is present in an amount of 30 to 50 wt.% of the bonding agent system is a drying oil. The term drying oil includes not only the actual drying oils but also the so- called semi-drying oils or the boiled oils, such as stand oils. Examples are linseed oil, soya oil, beet oil and stand oil. Such drying oils are described in more detail in Ullmans Encyclopedia of Technical Chemistry, Third Edition (1966) Volume 17, page 694 et seq.
The second component, which is present in an amount of 30 to 50 wt.% with respect to the entire bonding agent system, is an unsaturated fatty acid. Examples of such unsaturated fatty acids or oleic acid, linoleic acid and linolenic acid, though multiply unsaturated fatty acids can also be used. If these unsaturated fatty acids are not liquid they can be provided in a mixture with other, liquid and 4 unsaturated fatty acids or they can be dissolved in an organic solvent, e. g. a mineral oil or an alcohol such as methanol or ethanol or in benzene or chloroform.
The third component of the bonding agent system is a boron compound. Both borates and boric acid can be used but boron trif luoride adducts (BF3 adducts), as are described in DE-B-1261281, can also be used. The boron compound is used in an amount of 5 to 20 wt.%, calculated as B203. in the bonding agent system.
The fourth component of the bonding agent system comprises 5 to 20 wt.% of a heat-curable resin, resol resins and novolak resins being particularly preferred. However,, heat-curable furan resins or melamine resins can also be used.
is The invention will be described in more detail with reference to the following examples. Examples 1 to 5 Fired dolomite with a grain size distribution given in the following table was mixed in a mixer together with soot and flakey graphite and also solid boric acid.
The further components of the bonding agent system given in the following table were added to this mixture,, in each case to a 100 parts by weight, and -homogeneous compositions were produced. Mixing was conducted for 15 minute in a Hobart mixer and the compositions were subsequently subjected to testing of their compressability and hot compression strength.
The compressability was determined by loosely filling 275 g of the composition when ready for processing into a lightly oiled cylindrical mould with an internal diameter of 50 mm and a height of 140 mm. The ram was subsequently placed within the cylindrical mould on the sample material and the composition was compressed with four blows. The height of the test body after these four blows was determined and designated H4, Six further blows were then applied and the height of the test body was thereafter determined again, this height being designated H10.
The compressability was calculated in accordance with the following formula:
H4 - H10 X 100 H4 This measurement was conducted on three test bodies.
The hot compression strength was determined on test bodies which had been retained hot at 2800C for 15, 30 and 45 minutes, respectively, in a drying chamber. The hot test bodies were tested ny means of a press to determine the cold compression strength by compressing them to failure at a constant loading speed (1.0 + 0.1 N/mm2 sec.) The composition of the refractory compositions and the measured values determined on these refractory compositions are set forth in the following table:
6 Table
Example 1 2 3 4 5 Fired at 3-6mm (pts. by wt.) 10 20 20 20 20 dolomite 1-3mm VC 30 20 20 25 20 0.63-lmm It 30 30 40 25 20 <0.63mm 30 30 20 30 40 Soot 1 1 1 1 1 Flakey graphite 1 1 1 1 1 Stand oil 2.5 2.5 2.5 2.5 2.5 Oleic acid 2.0 2.0 2.0 2.0 2.0 Novolak resin 1 1 1 1 1 B203 1 1 1 1 1 Compressability 5.4 4.8 5.1 5.1 4.5 Breaking stress (N/mm2 After Drying time (280OC) 15 min 0.41 0.56 0.56 0.05 0.1o 0.66 0.87 0.87 0.81 1.27 3.06 3.67 4.43 3.72 3.67 7

Claims (3)

1 A refractory composition containing fired magnesite and/or fired dolomite as the principal refractory material and 2 to 8 wt.%, with respect to the weight of the entire composition, of a temporary bonding agent system comprising 30 to 50 wt.% of a drying oil, 30 to 50 wt.% of an unsaturated fatty acid, 5 to 20 wt.% of a boron compound and 5 to 20 wt.% of a heat-curable resin, the total of the components of the bonding agent system being 100 wt.%.
2. A composition as claimed in claim 1, which additionally contains 1 to 8 wt.%, with respect to the weight of the entire composition, of flakey graphite, soot and/or coke.
3. A refractory composition substantially as described in any one of the accompanying Examples.
Published 1989 atThe Patent O:Mce,State House, 6671 High Holborn,London WClFL4TP. Further copies maybe obtainedfrom The Patent Dffice Was Branch, St Mary Cray, Orpington, Kent BRS 3RD. Printed by Multiplex techniques ltd, St MsJ7 Cray, Kent, Com 1/87
GB8904513A 1988-03-01 1989-02-28 Refractory compositions containing magnesium oxide Expired - Fee Related GB2216116B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE3806563A DE3806563A1 (en) 1988-03-01 1988-03-01 MAGNESIUM OXYGEN-CONTAINING FIRE FIGURES

Publications (3)

Publication Number Publication Date
GB8904513D0 GB8904513D0 (en) 1989-04-12
GB2216116A true GB2216116A (en) 1989-10-04
GB2216116B GB2216116B (en) 1991-07-31

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GB8904513A Expired - Fee Related GB2216116B (en) 1988-03-01 1989-02-28 Refractory compositions containing magnesium oxide

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BE (1) BE1003073A3 (en)
DE (1) DE3806563A1 (en)
FR (1) FR2628098B1 (en)
GB (1) GB2216116B (en)
IT (1) IT1230494B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0669293A1 (en) * 1994-02-25 1995-08-30 North American Refractories Company Resin bonded ceramic-carbon-metal composite comprising boron source and a combination of at least two metals
WO2021104607A1 (en) * 2019-11-26 2021-06-03 Refractory Intellectual Property Gmbh & Co. Kg A composition and a method for the manufacture of a refractory lining on a surface

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2523993C3 (en) * 1975-05-30 1985-08-08 Sumitomo Metal Industries, Ltd., Osaka Refractory repair material for blast furnaces
US4383045A (en) * 1982-04-27 1983-05-10 Martin Marietta Corp. Magnesia refractories bonded with sulfamic acid
DE3304119A1 (en) * 1983-02-08 1984-08-09 Dolomitwerke GmbH, 5603 Wülfrath BASIC FIRE-RESISTANT MEASURES AND MOLDED BODIES

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0669293A1 (en) * 1994-02-25 1995-08-30 North American Refractories Company Resin bonded ceramic-carbon-metal composite comprising boron source and a combination of at least two metals
WO2021104607A1 (en) * 2019-11-26 2021-06-03 Refractory Intellectual Property Gmbh & Co. Kg A composition and a method for the manufacture of a refractory lining on a surface

Also Published As

Publication number Publication date
DE3806563A1 (en) 1989-09-14
FR2628098A1 (en) 1989-09-08
FR2628098B1 (en) 1992-04-10
BE1003073A3 (en) 1991-11-12
GB2216116B (en) 1991-07-31
GB8904513D0 (en) 1989-04-12
IT8947691A0 (en) 1988-02-27
DE3806563C2 (en) 1990-04-05
IT1230494B (en) 1991-10-24

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PCNP Patent ceased through non-payment of renewal fee

Effective date: 19930228