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WO2007079806A1 - Composition pour un produit ceramique refractaire et produit ceramique refractaire obtenu a partir de cette composition - Google Patents

Composition pour un produit ceramique refractaire et produit ceramique refractaire obtenu a partir de cette composition Download PDF

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Publication number
WO2007079806A1
WO2007079806A1 PCT/EP2006/010582 EP2006010582W WO2007079806A1 WO 2007079806 A1 WO2007079806 A1 WO 2007079806A1 EP 2006010582 W EP2006010582 W EP 2006010582W WO 2007079806 A1 WO2007079806 A1 WO 2007079806A1
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WIPO (PCT)
Prior art keywords
ceramic product
offset according
offset
refractory
mass
Prior art date
Application number
PCT/EP2006/010582
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German (de)
English (en)
Inventor
Christian Majcenovic
Dieter Pirkner
Original Assignee
Refractory Intellectual Property Gmbh & Co. Kg
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.)
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Publication date
Application filed by Refractory Intellectual Property Gmbh & Co. Kg filed Critical Refractory Intellectual Property Gmbh & Co. Kg
Priority to EP06806683A priority Critical patent/EP1966106A1/fr
Publication of WO2007079806A1 publication Critical patent/WO2007079806A1/fr

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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
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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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Definitions

  • the invention relates to an offset for a refractory under normal use ceramic product, such as a molding or a casting.
  • Refractory ceramic products both masses (such as castables, shotguns, ramming masses, mortar) and molded parts (such as bricks, cuboids, cones, plates) are used for lining metallurgical melting vessels as well as for use as functional parts (such as slide plates, sleeves, Plugs, lances, pipes), in particular in the context of secondary metallurgical processes.
  • masses such as castables, shotguns, ramming masses, mortar
  • molded parts such as bricks, cuboids, cones, plates
  • functional parts such as slide plates, sleeves, Plugs, lances, pipes
  • the refractory material comes into contact not only with the metallurgical melts but also with corresponding slags.
  • the refractory material is subject to considerable wear, in particular wear due to a chemical / metallurgical corrosion attack, wherein an infiltration of melt and / or slag into the refractory material may be a cause of wear.
  • additives which can lead to a reduction in the wear of the refractory material.
  • These additives which are said to make the finished refractory material more corrosion resistant and / or which better protect the refractory material from infiltration of contaminants, are hereinafter referred to as "corrosion / infiltration inhibitors.”
  • Barium sulfate (BaSO 4 ) and calcium fluoride (CaF 2 ) are such substances.
  • Barium sulfate decomposes at higher temperatures.
  • BaSO 4 reacts to Celsian (BaAl 2 Si 2 Oe) and the protective effect of the additive is lost. This is especially true in the temperature range> 900 ° C.
  • a refractory lining in a melting vessel may become hot during heating between 1100 and 1250 ° C. It is then often hotter than the subsequently treated in the vessel melt. BaSO 4 then fails completely as wear protection.
  • the invention is so far the object of demonstrating a way to improve the infiltration / corrosion behavior of refractory ceramic products, especially in the high-temperature application (> 1,200 ° C).
  • the calcium sulfate can be used anhydrous, ie as anhydrite (CaSO 4 ), or hydrous, for example as hemihydrate (CaSO 4 • Vi H 2 O) or dihydrate (CaSO 4 • 2H 2 O), as a fine powder or in various coarser particle fractions.
  • anhydrite CaSO 4
  • hydrous for example as hemihydrate (CaSO 4 • Vi H 2 O) or dihydrate (CaSO 4 • 2H 2 O), as a fine powder or in various coarser particle fractions.
  • Blaine's specific surface area may be> 2000 cm 2 / g. It can be over 4000 cm 2 / g and reach values> 7000 cm 2 / g.
  • the residue on a sieve according to DIN 4188 is then for example: R 0.02 mm:> 40%, R 0.02 mm> 25% or R 0.02 mm: ⁇ 20%.
  • Usually Blaine's specific surface area is> 1000 cm 2 / g.
  • the said corrosion-inhibiting substances are used as an offset component, optionally also added to the finished product, for example by infiltration by means of vacuum treatment.
  • the CaSO 4 decomposes, but forms new compounds with the surrounding refractory material, which are likewise infiltrations / corrosion inhibitors.
  • the reasons / phenomena are not fully understood yet. However, it was found, inter alia, that CaSO 4 reacts at higher temperatures with alumina from the refractory product to yeelimite (Ca 4 AloOi 2 SO 4 ). Yeelimit is stable up to> 1200 ° C and obviously takes over the protective function of the calcium sulfate additive at higher temperatures.
  • the invention comprises an offset for a refractory under normal use ceramic product, the
  • Basic refractory components are substances (compounds such as oxides) that are refractory or fire-resistant at higher temperatures (> 900 ° C). They are used according to the invention in grain sizes ⁇ 6 mm and may contain a fine grain fraction ( ⁇ 250 microns).
  • the raw material offset shall be adjusted accordingly, provided that the corrosion-inhibiting component (s) are not first introduced by impregnation of the finished fired product.
  • the offset thus contains corresponding additives (additives).
  • the amount of the infiltration-inhibiting component in the offset can be adjusted to ⁇ 15, ⁇ 10, ⁇ 7, ⁇ 5, to ⁇ 3% by mass, based on the total offset from the refractory base component and the admixture. Usually their share amounts to>1,> 3 or> 5 M .-%. Accordingly, the proportion of the refractory base component (sum of refractory base components and additives calculated in each case to 100% by mass) increases or decreases.
  • a binder e.g. based on phosphate or cement, or antioxidants (total of all offset components then added to 100 M .-%).
  • the invention includes the processing of the offset to ceramic bonded refractory products as well as the processing into chemically bonded products.
  • the refractory ceramic products may be monolithic compositions, mortars, moldings, for example in the form of stones, plates, sleeves or the like.
  • a suitable base component may at least partially be a non-basic basic component, for example from the group: alumina, corundum, ZrO 2 , zirconium silicate (ZrO 2 .SiO 2 ), mullite, TiO 2 , SiC, andalusite, chromium oxide, microsilica.
  • Cr 2 O 3 -free products are preferred.
  • BaSO 4 and / or CaF 2 can be dispensed with.
  • a suitable offset can be prepared in a conventional manner, for example by mixing the refractory base component (s) with the additive (s) and a binder, then shaping (for example by pressing) and firing for sintering, especially at temperatures> 1200 ° C ,
  • Example 3 Offset for a stone to be pressed
  • Example 1 From the offset according to Example 1 four test specimens of size 25x25x51 mm were prepared. The so-called “fill immersion test” was carried out on these test specimens, as it results from "Aluminum Transactions, Vol. 3, No. 1, 2000, 105-120", to which reference is made. The specimens were placed at a distance from each other on the bottom of a lined with silicon carbide casting compound test vessel, which was filled with 3.5 kg of an aluminum melt of the following specification so that the specimens were completely covered by the melt.
  • the surface of the molten bath was covered with a salt to prevent oxidation.
  • composition of aluminum melt is Composition of aluminum melt:

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Abstract

L’invention concerne une composition pour une application de manière appropriée d’un produit céramique réfractaire, par exemple un corps moulé ou un matériau de coulage.
PCT/EP2006/010582 2005-12-23 2006-11-04 Composition pour un produit ceramique refractaire et produit ceramique refractaire obtenu a partir de cette composition WO2007079806A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113387706A (zh) * 2021-04-22 2021-09-14 北京金隅通达耐火技术有限公司 一种余热锅炉水冷壁衬里用耐磨耐腐蚀碳化硅帽

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3552984A (en) * 1967-12-18 1971-01-05 Kaiser Aluminium Chem Corp Gunnable refractory
DE2344888A1 (de) * 1972-09-09 1974-04-04 Shoji Shimizu Verfahren zur herstellung spezifisch leichter, anorganischer feuerfester stoffe
DE3610586A1 (de) * 1984-09-21 1987-12-03 Denki Kagaku Kogyo Kk Bindemittel fuer ein feuerfestes material und dieses bindemittel enthaltendes feuerfestes produkt

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3552984A (en) * 1967-12-18 1971-01-05 Kaiser Aluminium Chem Corp Gunnable refractory
DE2344888A1 (de) * 1972-09-09 1974-04-04 Shoji Shimizu Verfahren zur herstellung spezifisch leichter, anorganischer feuerfester stoffe
DE3610586A1 (de) * 1984-09-21 1987-12-03 Denki Kagaku Kogyo Kk Bindemittel fuer ein feuerfestes material und dieses bindemittel enthaltendes feuerfestes produkt

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS + INDEXES, AMERICAN CHEMICAL SOCIETY. COLUMBUS, US, 11 March 1991 (1991-03-11), XP000187649, ISSN: 0009-2258 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113387706A (zh) * 2021-04-22 2021-09-14 北京金隅通达耐火技术有限公司 一种余热锅炉水冷壁衬里用耐磨耐腐蚀碳化硅帽

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