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WO2005061411A1 - Matiere refractaire coulable monolithique - Google Patents

Matiere refractaire coulable monolithique Download PDF

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Publication number
WO2005061411A1
WO2005061411A1 PCT/US2004/042861 US2004042861W WO2005061411A1 WO 2005061411 A1 WO2005061411 A1 WO 2005061411A1 US 2004042861 W US2004042861 W US 2004042861W WO 2005061411 A1 WO2005061411 A1 WO 2005061411A1
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Prior art keywords
refractory material
monolithic refractory
monolithic
dispersant
carbon black
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Ceased
Application number
PCT/US2004/042861
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English (en)
Inventor
Samuel B. Bonsall
George M. Stoupis
David A. Knowlton
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Vesuvius Crucible Co
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Vesuvius Crucible Co
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Publication of WO2005061411A1 publication Critical patent/WO2005061411A1/fr
Anticipated expiration legal-status Critical
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    • 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
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    • 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
    • C04B35/62605Treating the starting powders individually or as mixtures
    • C04B35/62645Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62665Flame, plasma or melting treatment
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    • 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
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    • 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
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    • 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
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    • 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
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    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
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    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • 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
    • C04B2235/3217Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3222Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
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    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
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    • C04B2235/38Non-oxide ceramic constituents or additives
    • C04B2235/3817Carbides
    • C04B2235/3826Silicon carbides
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    • 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
    • C04B2235/424Carbon black
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    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
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    • C04B2235/42Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422Carbon
    • C04B2235/425Graphite
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    • 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
    • C04B2235/48Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
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    • 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
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5427Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
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    • 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
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436Particle 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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    • C04B2235/00Aspects 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
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron

Definitions

  • the present invention relates to monolithic refractory materials, and in particular a low- toxicity castable refractory having excellent corrosion resistance and spalling resistance. Description of the related art.
  • monolithic refractory materials are often used as linings for vessels such as ladles that transport the molten metal throughout the process.
  • carbon-bonded materials are typically used.
  • the monolithic refractories generally comprise a refractory aggregate and a binder.
  • Various binders have been used throughout the years, including binders utilizing coal tar pitch.
  • U.S. Patent No. 4,184,883 discloses a pitch-bonded refractory that utilizes a cure accelerator such as calcium nitrate to accelerate the rate of increase of the softening point of the pitch in order to decrease the amount of spalling that occurs during burn-in and the early heats of the refractory.
  • U.S. Patent No. 5,866,490 utilizes a pitch as a binder, the pitch having a high percentage of fixed carbon, as well as a high softening point. This is done in an effort to increase carbon bonding in order to prevent corrosion and spalling of the refractory.
  • this reference also teaches the use of a phenol resin or a carbon fiber in addition to the pitch binder.
  • coal tar pitch is a very toxic material, and when the material is heated, the toxic vapors can be released into the atmosphere. This requires the use of expensive safety equipment for those people working near the refractory material, as well as environmental safeguards to prevent the release of the toxic material into the air. Further, coal tar pitch is a known carcinogen, and therefore elimination of the material is generally desirable.
  • monolithic refractory material having good corrosion resistance and spalling resistance, but without the use of a coal tar pitch-based binder. Summary of the invention. [0007] In order to achieve the listed objectives, monolithic refractory material is provided in accordance with the present invention.
  • the refractory material comprises refractory aggregate and a binder, the binder comprising petroleum pitch and carbon black.
  • the binder may further comprise graphite.
  • a monolithic refractory material comprising a refractory aggregate and a binder, characterized in that the binder comprises carbon black and petroleum pitch.
  • the refractory aggregate comprises brown fused alumina and silicon carbide
  • the petroleum pitch has a mass particle size wherein 50 to 70% is smaller than 75 micrometers and has a carbon yield of about 45% to about 55%.
  • the carbon black has an average particle size of about 200 nanometers to about 400 nanometers and an ash content of less than about 0.25% of the mass of the carbon black.
  • a monolithic refractory material comprising a refractory aggregate and a binder, characterized in that the binder comprises carbon black and petroleum pitch, the petroleum pitch has a mass particle size wherein 50 to 70% is smaller than 75 micrometers and has a carbon yield of about 45% to about 55%, and the carbon black has an average particle size of about 200 nanometers to about 400 nanometers and an ash content of less than about 0.25% of the mass of the carbon black.
  • FIG. 1 is a graphical comparison of carbon retention with refractories utilizing coal tar pitch and petroleum pitch, with and without added carbon black. Detailed description of the preferred embodiments.
  • the present invention is a monolithic refractory comprising a refractory aggregate and a binder, the binder comprising petroleum pitch and carbon black.
  • the refractory may further comprise a dispersant.
  • the refractory comprises about 1.0 to about 3.0% petroleum pitch, about 0.5% to about 1.5% carbon black, with the balance being a refractory aggregate.
  • the refractory may also contain graphite to further increase the carbon content.
  • the refractory further comprises about 0.0 % to about 0.15% of a dispersant.
  • the refractory aggregate used in accordance with the present invention may be any one of the refractory aggregates known by those in the art to be suitable for the present applications.
  • Suitable refractory aggregates include, for example, brown fused alumina, bauxite, tabular alumina, silicon carbide, calcined bauxitic kaolins (such as Mulcoa 70, Mulcoa 60, and Mulcoa 47), andalusite, calcined fireclay, and combinations thereof.
  • the refractory aggregate is present in amounts that depend on the amount of binder desired. However, the refractory aggregate will make up most of the material present in the monolithic refractory.
  • the particle size for the aggregate is based on the principles of optimum particle packing commonly used to formulate ultra low cement castables.
  • the maximum aggregate particle size is about 9.5 millimeters, with a minimum size of about 45 microns.
  • the petroleum pitch used in accordance with the present invention accounts for about 1.0% to about 3.0% of the monolithic refractory.
  • the petroleum pitch is preferably characterized by a mass particle size wherein 50-75%, typically 70% is smaller than about 75 micrometers.
  • the petroleum pitch is also characterized by a carbon yield. Carbon yield is defined as the percent by weight of the pitch that is left as a carbonized residue after the pitch is heated under non-oxidizing conditions to about 800-1000°C to drive off volatiles.
  • the petroleum pitches used may have a carbon yield of about 45% to about 55%.
  • the petroleum pitch is characterized by a carbon yield of about 49%.
  • the carbon black used in accordance with the present invention accounts for about 0.5% to about 1.5% of the monolithic refractory.
  • the carbon black has an average particle size of about 200 nanometers to about 400 nanometers.
  • the carbon black has an average particle size of about 300 nanometers.
  • the carbon black is also characterized by an ash content of less than about 0.25% of the mass of the carbon black. It should be noted that as the amount of carbon black used increases, the amount of water that must be included also increases. This may limit the amount of carbon black that can be incorporated into the monolithic refractory. Graphite may be added to increase the carbon level beyond the limit for carbon black alone.
  • the monolithic refractory may further comprise a dispersant. If used, the dispersant accounts for about 0.01 % to about 0.15% of the monolithic refractory.
  • Suitable dispersants include sodium lignosulfonate, other lignosulfonate salts (Ca, K, etc.), or Sodium, potassium and Calcium salts of condensed naphthalene sulfonic acids.
  • a wet sprayable refractory comprising brown fused alumina, silicon carbide, calcium aluminate cement, petroleum pitch, carbon black and a sodium lignosulfonate dispersant powder.
  • the petroleum pitch was a pitch commercially available under the name "Trolumen” from Smith-Facing of Cleveland, OH, having 70% finer than 75 micrometers and
  • the pitch made up 2.33% of the refractory.
  • the carbon black made up 1 % of the refractory and is available from Asbury Carbon of Asbury, NJ, and sold as #5991.
  • the sodium lignosulfonate dispersant powder made up 0.05% of the refractory and is available from Lignotech of Rothschild, Wl under the name "Ultrazine NA.”
  • the balance of the refractory was the aggregate (brown fused alumina, silicon carbide and calcium aluminate cement).
  • the refractory was subjected to 1500° F for 5 hours, along with a similar refractory containing coal tar pitch instead of petroleum pitch, a similar refractory without carbon black, and a refractory without carbon black and with coal tar pitch instead of petroleum pitch, in the same amount.
  • the carbon retention was measured for all 4 refractories. As illustrated in Fig. 1 , the % carbon retention for the two refractories with petroleum pitch, while lower, was acceptably similar to the two refractories using coal tar pitch. Further, the refractories utilizing the carbon black had higher carbon retention than the two without the carbon black.

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

Abstract

L'invention porte sur une matière réfractaire monolithique. La matière réfractaire de l'invention comprend un granulat réfractaire et un liant, le liant comprenant du brai de pétrole et du noir de carbone. Le liant peut avantageusement comprendre aussi du graphite.
PCT/US2004/042861 2003-12-18 2004-12-17 Matiere refractaire coulable monolithique Ceased WO2005061411A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US53083103P 2003-12-18 2003-12-18
US60/530,831 2003-12-18

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WO2005061411A1 true WO2005061411A1 (fr) 2005-07-07

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8026191B2 (en) * 2007-01-26 2011-09-27 Wonjin Worldwide Co., Ltd. Carbon-containing refractory composition containing no resinous binder
CN102826862A (zh) * 2012-09-04 2012-12-19 山西新型炉业集团有限公司 一种铝矾土基致密均化料的原料配比及生产方法
CN108821784A (zh) * 2018-06-19 2018-11-16 佘春霞 一种高炭黑环保主沟浇注料

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4071593A (en) * 1973-11-06 1978-01-31 General Refractories Company Process for making a pitch impregnated, cold molded refractory article
US4184883A (en) * 1976-12-17 1980-01-22 Eltra Corporation Pitch bonded refractory
US4521357A (en) * 1983-05-02 1985-06-04 Dresser Industries, Inc. Carbon bonded refractories
US4558019A (en) * 1984-01-20 1985-12-10 Allied Corporation Periclase refractory brick with oxyhydrocarbon component
US4585485A (en) * 1983-01-24 1986-04-29 Hiroshi Shikano Refractory sliding nozzle plate
US4605635A (en) * 1984-01-17 1986-08-12 Shinagawa Refractories Co., Ltd. Carbon-containing refractory
US5304225A (en) * 1990-05-15 1994-04-19 Rutgerswerke Ag Binder mixture
US5346942A (en) * 1989-10-11 1994-09-13 Shinagawa Refractories Co., Ltd. Monolithic refractories
US6288001B1 (en) * 1997-12-25 2001-09-11 Kawasaki Steel Corporation Graphite-containing monolithic refractory material

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4071593A (en) * 1973-11-06 1978-01-31 General Refractories Company Process for making a pitch impregnated, cold molded refractory article
US4184883A (en) * 1976-12-17 1980-01-22 Eltra Corporation Pitch bonded refractory
US4585485A (en) * 1983-01-24 1986-04-29 Hiroshi Shikano Refractory sliding nozzle plate
US4521357A (en) * 1983-05-02 1985-06-04 Dresser Industries, Inc. Carbon bonded refractories
US4605635A (en) * 1984-01-17 1986-08-12 Shinagawa Refractories Co., Ltd. Carbon-containing refractory
US4558019A (en) * 1984-01-20 1985-12-10 Allied Corporation Periclase refractory brick with oxyhydrocarbon component
US5346942A (en) * 1989-10-11 1994-09-13 Shinagawa Refractories Co., Ltd. Monolithic refractories
US5304225A (en) * 1990-05-15 1994-04-19 Rutgerswerke Ag Binder mixture
US6288001B1 (en) * 1997-12-25 2001-09-11 Kawasaki Steel Corporation Graphite-containing monolithic refractory material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8026191B2 (en) * 2007-01-26 2011-09-27 Wonjin Worldwide Co., Ltd. Carbon-containing refractory composition containing no resinous binder
CN102826862A (zh) * 2012-09-04 2012-12-19 山西新型炉业集团有限公司 一种铝矾土基致密均化料的原料配比及生产方法
CN108821784A (zh) * 2018-06-19 2018-11-16 佘春霞 一种高炭黑环保主沟浇注料

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