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WO2011115353A1 - Matériau réfractaire non façonné lié à de l'alumine et son procédé de fabrication - Google Patents

Matériau réfractaire non façonné lié à de l'alumine et son procédé de fabrication Download PDF

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Publication number
WO2011115353A1
WO2011115353A1 PCT/KR2010/008502 KR2010008502W WO2011115353A1 WO 2011115353 A1 WO2011115353 A1 WO 2011115353A1 KR 2010008502 W KR2010008502 W KR 2010008502W WO 2011115353 A1 WO2011115353 A1 WO 2011115353A1
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Prior art keywords
alumina
bonded
unshaped refractory
refractory
unshaped
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Inventor
Kyoung Ran Han
Sang Whan Park
Chang Sam Kim
Jin Oh Yang
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Korea Institute of Science and Technology KIST
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Korea Institute of Science and Technology KIST
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Publication of WO2011115353A1 publication Critical patent/WO2011115353A1/fr
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Definitions

  • the present disclosure relates to an alumina-bonded unshaped refractory and a method for manufacturing the same. More particularly, the disclosure relates to an alumina-bonded unshaped refractory with high strength without cement, which can be used for a blast furnace or a slag contacting part of a gasifier, and a method for manufacturing the same.
  • Refractories are used in combustion furnaces, gasifiers or blast furnaces to increase resistance against thermal shock, erosion, corrosion, or the like. They are used in the form of refractory bricks or unshaped refractories. Unshaped refractories are preferred over refractory bricks where the gap between the bricks becomes a problem. Thus, various efforts have been made to improve high temperature durability material properties and installations of the unshaped refractories.
  • the unshaped refractory is manufactured by binding refractory aggregates and fine powder with a binder.
  • calcium aluminate cement has been predominantly used as the binder, low calcium aluminate cement is preferred for use in harsh environments such as high temperature and high pressure conditions.
  • hydratable alumina containing low calcium has been used for unshaped refractory in order to improve resistance to thermomechanical wearng and corrosion.
  • it also showed relatively low strength (flexural strength of 1.2-2.0 MPa ) at a temperature of 800 to 1200 oC, where water that maintains binding is dehydrated while ceramic bonding is not yet significantly formed.
  • the sintered refractory has a flexural strength not greater than 20 MPa.
  • a gasifier used in an integrated gasification combined cycle (IGCC) of coal which is gaining attentions as an efficient, environment-friendly power generation system, is operated under a harsh condition.
  • An unshaped refractory used in the lining of the gasifier requires to be adhered well to a stainless steel pipe through which cooling water flows, have good thermal conductivity and allow easy formation of a slag layer on the surface.
  • the unshaped refractory is prepared by binding refractory aggregate, matrix with aluminate cement.
  • the cement content is low, the density of the resulting refractory becomes low, and it becomes difficult to handle and control of drying time. Meanwhile, the low cement content improves corrosion resistance against slag and slows penetration. This is because calcium oxide (CaO) included in the cement reacts with the slag at high temperature and lowers the viscosity of the slag, thereby allowing the slag to easily penetrate and corrode the refractory.
  • CaO calcium oxide
  • cement is not advantageous in that it requires a lengthy time for drying at room temperature because of slow water evaporation.
  • P 2 O 5 -MgO system produces problems that low-melting-point compounds are produced and the water-soluble monoaluminum phosphate migrates to the surface, resulting in non-uniform strength.
  • P 2 O 5 evaporates in a high temperature reducing environment, resulting in reduced and non-uniform strength. Accordingly, the aluminum phosphate-bonded unshaped refractory is not suitable for forming a refractory structure.
  • hydratable alumina has been used as an inorganic binder.
  • Alphabond 100, 300, 500, etc. are commercially available from Alcoa Industrial Chemicals.
  • the hydratable alumina binder is not advantageous in that it requires a longer mixing time until wet-out is achieved.
  • Alphabond 500 of larger alumina particles than Alphabond 300 were used to reduce the mixing time.
  • the fluidity of the unshaped refractory is greatly affected by the amount of fine powder.
  • the hydratable alumina binder is used in an amount of 3 to 7 wt%.
  • the currently used hydratable alumina consists mainly of ⁇ -alumina powder as well as ⁇ -alumina that readily reacts with water and a small amount of CaO and SiO 2 .
  • the average particle size of ⁇ -alumina is 2.3 ⁇ m and CaO content is less than 0.1 wt%.
  • the average particle size is 5.2 ⁇ m and CaO content is 0.6 wt%. If the CaO content is low, the refractory has a weak strength at room temperature.
  • the hydratable alumina is used either alone or in combination with a small amount of silica or calcium aluminate cement. The hydratable alumina is not advantageous in that its performance is deteriorated upon exposure to moisture in the air and the strength of the refractory decreases when mixed at 15 oC or below.
  • the conventional unshaped refractories are hardly applicable at high temperature and high pressure under oxygen-deficient atmosphere, and also have low strength at room temperature.
  • the inventors have manufactured an alumina-bonded unshaped refractory using alumina precursor powder instead of cement and have confirmed that the alumina-bonded unshaped refractory has sufficient strength, experiences little contraction after heat treatment and exhibits low porosity and high strength.
  • the present disclosure provides an alumina-bonded unshaped refractory including Al 2 O 3 , SiC, alumina precursor powder and water.
  • the present disclosure provides a method for manufacturing an alumina-bonded unshaped refractory, including: (a) mixing Al 2 O 3 , SiC and alumina precursor powder to prepare a refractory mixture; (b) adding water to the refractory mixture to obtain a mixture; (c) curing and drying the mixture; and (d) heat-treating the cured and dried mixture.
  • the alumina-bonded unshaped refractory according to the present disclosure is advantageous in that drying is fast and cracking does not occur during drying and heat treatment. Further, it can be used at high temperature because calcium oxide (CaO) is not included, and has high strength and density. Thus, it may effectively replace the conventional unshaped refractory using cement.
  • CaO calcium oxide
  • the present disclosure provides an alumina-bonded unshaped refractory.
  • alumina precursor powder capable of providing binding to a mixture of Al 2 O 3 and SiC and providing strength is added as an inorganic binder precursor. After the powder is uniformly distributed on the refractory surface, water or water and an additive is added to obtain the alumina-bonded unshaped refractory.
  • the alumina-bonded unshaped refractory according to the present disclosure is manufactured as follows.
  • the present disclosure provides a method for manufacturing an alumina-bonded unshaped refractory, including: (a) mixing Al 2 O 3 , SiC and alumina precursor powder to prepare a refractory mixture; (b) adding water to the refractory mixture to obtain a refractory castable; (c) curing and drying the castable; and (d) heat-treating the cured and dried castable to improve strength.
  • the refractory mixture is prepared by mixing aluminum oxide (Al 2 O 3 ) and silicon carbide (SiC) with alumina precursor powder which serves as an inorganic binder precursor.
  • Al 2 O 3 is one of the aggregate components of the refractory and plays an important role in maintaining high flexural strength during the manufacture of the alumina-bonded unshaped refractory.
  • particle diameter and particle mixing proportion of Al 2 O 3 are not particularly limited.
  • SiC is another aggregate component of the refractory. Being insoluble in water or acids, chemically inert and very hard, it prevents corrosion and wearing when the molten slag flows along the refractory wall, thereby improving durability.
  • SiC may be coarse aggregate (particle diameter: 1 to 6 mm), fine aggregate (particle diameter: 50 ⁇ m to 1 mm) or fine powder (particle diameter: 50 ⁇ m or smaller), and the particle mixing proportion is not particularly limited.
  • a mixture of Al 2 O 3 and SiC is used.
  • the mixing proportion is not particularly limited, but it may be between 10 : 90 and 30 : 70 based on weight.
  • Alumina precursor powder is mixed with the mixture of Al 2 O 3 and SiC and uniformly distributed.
  • the alumina precursor powder which serves as an inorganic binder precursor is easily dispersed in water at room temperature to form a semi-transparent alumina sol. Accordingly, when the alumina precursor powder is mixed with Al 2 O 3 and SiC and added with water, the alumina precursor is hydrolyzed and polymerized and thus serves as an inorganic binder. Thus, the unshaped refractory can be prepared easily.
  • the alumina precursor powder may be ⁇ -alumina or boehmite, more specifically boehmite.
  • the alumina precursor powder may be used in an amount of 1 to 10 parts by weight, specifically 1 to 6 parts by weight, based on 100 parts by weight of Al 2 O 3 plus SiC. If the content of the alumina precursor powder is less than 1 part by weight, binding ability among the refractory mixture may decrease. In contrast, if it exceeds 10 parts by weight, more water has to be used for mixing, which results in increase in drying time, porosity due to the evaporation of water, and binding layer thickness, thereby making the unshaped refractory more vulnerable to corrosion by the slag.
  • the refractory mixture comprising Al 2 O 3, SiC and alumina precursor powder may further comprise 0.1 to 1.0 part by weight of spinel, magnesia or zirconia based on 100 parts by weight of Al 2 O 3 plus SiC.
  • the spinel, magnesia or zirconia is used to improve flexural strength of the alumina-bonded unshaped refractory.
  • water is added to the refractory mixture to obtain a castable mixture.
  • Water aids in hydrolysis and polymerization of the alumina precursor, so that the alumina precursor may serve as the inorganic binder.
  • Water may be used in an amount of 3 to 15 parts by weight, more specifically 4 to 10 parts by weight, based on 100 parts by weight of Al 2 O 3 plus SiC. If water is used in an amount less than 3 parts by weight, mixing and hydrolysis may be insufficient. In contrast, if it is used in an amount exceeding 15 parts by weight, drying time increases, layer separation may occur, and porosity may increase due to the evaporation of water.
  • the mixture to which water is added may further comprise an organic binder.
  • the organic binder aids in binding, thereby improving strength and providing an alumina-bonded unshaped refractory with more uniform structure.
  • the organic binder may be used in an amount of 0.01 to 5 parts by weight, more specifically 0.02 to 3 parts by weight, based on 100 parts by weight of Al 2 O 3 plus SiC. If it is used in an amount less than 0.01 part by weight, binding ability may decrease. In contrast, if it is used in an amount exceeding 5 parts by weight, porosity may increase due to decomposition and combustion during heat treatment.
  • the organic binder may be in the form of an aqueous solution.
  • hydroxyethyl cellulose HEC
  • methyl cellulose hydroxymethyl cellulose
  • hydroxypropyl cellulose or latex may be used. More specifically, hydroxyethyl cellulose may be used.
  • alumina-bonded unshaped refractory is cured and dried.
  • the curing may be performed at room temperature (15 to 40 oC) for 2 to 6 hours.
  • the drying may be performed at 60 to 100 oC for 3 to 4 hours.
  • the dried alumina-bonded unshaped refractory is heat-treated.
  • the heat treatment may be performed at 1350 to 1400 oC for 2 to 4 hours.
  • a refractory mixture was prepared in a polypropylene container as specified in Table 1.
  • 50 g of Composition 2 was put into a paper cup and 6.48 g of distilled water was added. Then, an unshaped material was prepared by tapping. After drying at room temperature (25 oC) for 2 hours and further drying in a 60 oC dryer for 4 hours, the unshaped material was heat treated at 1400 oC for 2 hours in the air. Flexural strength and density of thus prepared alumina-bonded unshaped refractory were measured. The result is given in Table 2.
  • An alumina-bonded unshaped refractory was prepared in the same manner as in Example 1, except that 50 g of Composition 2 was put into a paper cup, 8.5 g of 5 wt% hydroxyethyl cellulose (HEC) aqueous solution was added and heat treatment was performed at 1400 oC for 4 hours. Flexural strength and density were measured. The result is given in Table 2.
  • HEC hydroxyethyl cellulose
  • An alumina-bonded unshaped refractory was prepared in the same manner as in Example 1, except that 50 g of Composition 3 was put into a paper cup and 5.89 g of distilled water was added. Flexural strength and density were measured. The result is given in Table 2.
  • An alumina-bonded unshaped refractory was prepared in the same manner as in Example 1, except that 50 g of Composition 3 was put into a paper cup and 5.98 g of distilled water was added. Flexural strength and density were measured. The result is given in Table 2.
  • An alumina-bonded unshaped refractory was prepared in the same manner as in Example 1, except that 50 g of Composition 3 was put into a paper cup, 6.33 g of distilled water was added and heat treatment was performed at 1400 oC for 4 hours. Flexural strength and density were measured. The result is given in Table 2.
  • An alumina-bonded unshaped refractory was prepared in the same manner as in Example 1, except that 50 g of Composition 3 was put into a paper cup, 8.55 g of 5 wt% HEC aqueous solution was added and sintering was performed at 1400 oC for 4 hours. Flexural strength and density were measured. The result is given in Table 2.
  • An alumina-bonded unshaped refractory was prepared in the same manner as in Example 1, except that 50 g of Composition 4 was put into a paper cup and 6.81 g of distilled water was added. Flexural strength and density were measured. The result is given in Table 2.
  • An alumina-bonded unshaped refractory was prepared in the same manner as in Example 1, except that 50 g of Composition 4 was put into a paper cup, 7.67 g of distilled water was added and heat treatment was performed at 1400 oC for 4 hours. Flexural strength and density were measured. The result is given in Table 2.
  • An alumina-bonded unshaped refractory was prepared in the same manner as in Example 1, except that 50 g of Composition 1 was put into a paper cup and 10 g of 5 wt% HEC aqueous solution was added. Flexural strength and density were measured. The result is given in Table 2.
  • a refractory mixture comprising 0.4 g of spinel was mixed in a polypropylene container as specified in Table 3.
  • An alumina-bonded unshaped refractory was prepared in the same manner as in Example 1, except that 50 g of Composition 6 was put into a paper cup and 0.08 g of polyvinyl alcohol (PVA) was added. Flexural strength and density were measured. The result is given in Table 4.
  • composition of refractory mixturecomprisingspinel and boehmite content Al 2 O 3 (g) SiC (g) Spinel (g) Boehmite (g) d 50 3-5 mm 0.3 ⁇ m 1.25 mm 750 ⁇ m 90 ⁇ m 20 ⁇ m 5 ⁇ m ⁇ 44 ⁇ m Comp. 5 6.7 7.2 36.5 22.1 2.9 19.2 1.3 0.4 0 Comp. 6 7.0 7.2 36.5 22.6 3.0 19.7 1.3 0.4 2.0 Comp. 7 6.7 7.2 36.6 22.1 2.9 19.5 1.3 0.4 4.3
  • An alumina-bonded unshaped refractory was prepared in the same manner as in Example 1, except that 50 g of Composition 6 was put into a paper cup and 6.66 g of distilled water was added. Flexural strength and density were measured. The result is given in Table 4.
  • An alumina-bonded unshaped refractory was prepared in the same manner as in Example 1, except that 50 g of Composition 6 was put into a paper cup and 6.25 g of distilled water was added. Flexural strength and density were measured. The result is given in Table 4.
  • An alumina-bonded unshaped refractory was prepared in the same manner as in Example 1, except that 50 g of Composition 7 was put into a paper cup and 5.55 g of distilled water was added. Flexural strength and density were measured. The result is given in Table 4.
  • An alumina-bonded unshaped refractory was prepared in the same manner as in Example 1, except that 50 g of Composition 7 was put into a paper cup and 7.7 g of distilled water and 0.08 g of 5 wt% HEC aqueous solution were added. Flexural strength and density were measured. The result is given in Table 4.
  • An alumina-bonded unshaped refractory was prepared in the same manner as in Example 1, except that 50 g of Composition 5 was put into a paper cup and 8.8 g of 5 wt% HEC aqueous solution were added. Flexural strength and density were measured. The result is given in Table 4.

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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)
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Abstract

La présente invention concerne un matériau réfractaire non façonné lié à de l'alumine et son procédé de fabrication. Ledit matériau réfractaire non façonné lié à de l'alumine comprend de l'Al2O3, du SiC, un précurseur d'alumine en poudre et de l'eau. Ledit matériau réfractaire non façonné lié à de l'alumine présente une résistance suffisante, se contracte peu sous l'effet d'un traitement thermique et présente une faible porosité et une grande résistance, sans utilisation de ciment.
PCT/KR2010/008502 2010-03-16 2010-11-30 Matériau réfractaire non façonné lié à de l'alumine et son procédé de fabrication Ceased WO2011115353A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE212016000021U1 (de) 2015-12-16 2017-06-07 Calderys France Giessbare feuerfeste Zusammensetzungen, umfassend Zeolithmikrostrukturen, und Verwendungen davon
WO2025038311A1 (fr) * 2023-08-14 2025-02-20 Henkel Ag & Co. Kgaa Composition réfractaire

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101303812B1 (ko) * 2012-03-30 2013-09-04 한국과학기술연구원 석탄슬래그 침식에 강한 알루미나 코팅 스핀넬/탄화규소 내화물 조성물 및 이의 제조방법
KR101321944B1 (ko) * 2012-03-30 2013-11-04 한국과학기술연구원 무시멘트 고강도 부정형 내화물

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0211233A1 (fr) * 1985-07-02 1987-02-25 Nippon Shokubai Kagaku Kogyo Co., Ltd Catalyseur d'épuration des gaz d'échappement et procédé de fabrication
US5165996A (en) * 1990-05-08 1992-11-24 E. I. Du Pont De Nemours And Company Coated refractory compositions and method for preparing the same
JP2004063599A (ja) * 2002-07-25 2004-02-26 Matsushita Electric Ind Co Ltd 不燃化バリスタとその製造方法
US20060266673A1 (en) * 2005-05-25 2006-11-30 Rende Dean E Layered composition and processes for preparing and using the composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0211233A1 (fr) * 1985-07-02 1987-02-25 Nippon Shokubai Kagaku Kogyo Co., Ltd Catalyseur d'épuration des gaz d'échappement et procédé de fabrication
US5165996A (en) * 1990-05-08 1992-11-24 E. I. Du Pont De Nemours And Company Coated refractory compositions and method for preparing the same
JP2004063599A (ja) * 2002-07-25 2004-02-26 Matsushita Electric Ind Co Ltd 不燃化バリスタとその製造方法
US20060266673A1 (en) * 2005-05-25 2006-11-30 Rende Dean E Layered composition and processes for preparing and using the composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE212016000021U1 (de) 2015-12-16 2017-06-07 Calderys France Giessbare feuerfeste Zusammensetzungen, umfassend Zeolithmikrostrukturen, und Verwendungen davon
DE212016000023U1 (de) 2015-12-16 2017-06-08 Calderys France Giessbare feuerfeste Zusammensetzungen, umfassend Zeolithmikrostrukturen, und Verwendungen davon
WO2025038311A1 (fr) * 2023-08-14 2025-02-20 Henkel Ag & Co. Kgaa Composition réfractaire

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