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WO2013032065A1 - Matériaux réfractaires non façonnés résistant à la corrosion à faible teneur en ciment - Google Patents

Matériaux réfractaires non façonnés résistant à la corrosion à faible teneur en ciment Download PDF

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WO2013032065A1
WO2013032065A1 PCT/KR2011/008188 KR2011008188W WO2013032065A1 WO 2013032065 A1 WO2013032065 A1 WO 2013032065A1 KR 2011008188 W KR2011008188 W KR 2011008188W WO 2013032065 A1 WO2013032065 A1 WO 2013032065A1
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alumina
refractory
cement
zircon
unshaped
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PCT/KR2011/008188
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Kyoung Ran Han
Sang Whan Park
Chang Sam Kim
Hak Man Lee
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Korea Institute Of Science And Technology
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Definitions

  • the present invention relates to an unshaped refractory containing zircon, cement and an alumina binder that can be used in the lining of a gasifier.
  • Unshaped refractories are preferred to refractory bricks having the problem of gaps between the bricks, and improvements are made in terms of lifespan, material and construction method.
  • calcium aluminate cement has been predominantly used as inorganic binder, low-calcium aluminate cement is preferred as the operation environment becomes harsher (e.g., higher temperature and pressure).
  • hydratable alumina with a trace amount of calcium is used in unshaped refractories in order to improve resistance to thermal wear and corrosion.
  • this refractory has low strength (1.2-2.0 MPa) at 800-1200 oC where dehydration occurs and binding between ceramics disappear.
  • a gasifier used in the integrated gasification combined cycle (IGCC) technology which is valued highly as an ecofriendly power generation system recently, is operated under harsh environments. Since a stainless steel pipe through which cooling water flows is attached to an unshaped refractory used in the lining of the gasifier, the unshaped refractory should allow good attachment of the stainless steel pipe, have good thermal conductivity, and allow easy formation of a slag layer initially.
  • the unshaped refractory is made of oxide, carbide or a mixture thereof as a refractory as well as alumina cement as a binder.
  • the as-pressed refractory has a low density and is difficult to handle and the control of drying time is difficult, although resistance to slag corrosion and penetration is improved. It is because calcium oxide (CaO) included in the cement reacts at high temperature with the slag, allowing the slag easily penetrate into the refractory by decreasing viscosity. Further, since evaporation of water from the cement occurs slowly, sufficient drying is necessary at room temperature.
  • CaO calcium oxide
  • phosphate-based unshaped refractories are used. For example, one using monoaluminum phosphate as a binder and magnesium oxide (MgO) as a hardening agent is used for a combustion furnace.
  • hydratable alumina is used as an inorganic binder.
  • Commercially available ones include AlphaBond 300 and 500 of Alcoa Industrial Chemicals.
  • the refractory including the hydratable alumina binder requires a long mixing time.
  • bending strength at room temperature is only 5-17 MPa.
  • the unshaped refractory includes 7-10 wt% of ultrafine reactive alumina and at least 20 wt% of fine particulate powder including silica in addition to aggregate in order to improve flowability.
  • the existing refractories are unsuited for use in the high-temperature, high-pressure environment of the gasifier because of the problems of adhesivity, thermal conductivity, drying time, corrosion resistance, etc. , as well as strength.
  • the inventors of the present invention have studied for a refractory that can be used under the harsh environment of high temperature and pressure of a gasifier, and developed a refractory having superior adhesivity, strength, thermal conductivity and corrosion resistance.
  • the present invention is directed to providing an unshaped refractory including a refractory mixture of alumina (Al 2 O 3 ) and silicon carbide (SiC) to which one or more of alumina cement, zircon and an alumina binder is added.
  • alumina Al 2 O 3
  • SiC silicon carbide
  • the present invention provides an unshaped refractory including a refractory mixture of alumina (Al 2 O 3 ) and silicon carbide (SiC) to which one or more of alumina cement, zircon and an alumina binder is added.
  • alumina Al 2 O 3
  • SiC silicon carbide
  • a small amount of the cement and alumina binder provides working flowability to the refractory mixture, and a small amount of the zircon significantly prevents corrosion by the calcium oxide (CaO) included in the cement in an amount of about 20%. Since the refractory of the present invention maintains shape after drying, has sufficient strength for handling, exhibits little shrinkage after heat treatment and shows low porosity, it is particularly suited for use in the gasifier.
  • the alumina binder is mixed with the fine particulate alumina and coats the surface of the refractory like glue, improving contact between the refractories and facilitating evaporation of water as the sol transforms into gel.
  • the alumina gel film formed from the small amount of alumina binder prevents cracking during drying even when the heating speed is fast and facilitates sintering of the fine particulate alumina powder, thereby proving high strength resulting from ceramic binding between the refractories.
  • Fig. 1 shows a cross-sectional photographic image of a refractory sample of Comparative Example 1 comprising only an alumina binder after slag corrosion test.
  • Fig. 2 shows a cross-sectional photographic image of a refractory sample of Example 6 comprising 2 wt% of zircon, 3 wt% of cement and an alumina binder after slag corrosion test.
  • Fig. 3 shows a cross-sectional photographic image of a refractory sample of Comparative Example 2 comprising 3 wt% of alumina cement after slag corrosion test.
  • the present invention provides an unshaped refractory comprising a refractory mixture of alumina (Al 2 O 3 ) and silicon carbide (SiC) to which alumina cement, zircon, an alumina binder or a mixture thereof is added.
  • alumina Al 2 O 3
  • SiC silicon carbide
  • magnesium oxide, spinel, zirconia, chromia, hafnium oxide or a mixture thereof is further added to the refractory mixture of alumina (Al 2 O 3 ) and silicon carbide (SiC).
  • the alumina binder is included in an amount of 0.5-4 parts by weight based on alumina per 100 parts by weight of the total unshaped refractory comprising alumina (Al 2 O 3 ) and silicon carbide (SiC).
  • the alumina cement comprises 10-30 wt% of calcium oxide (CaO).
  • the alumina cement is added in an amount of 0.5-5 wt% based on the total weight of the unshaped refractory.
  • the zircon is added in an amount of 1-5 wt% based on the total weight of the unshaped refractory.
  • a hydratable alumina binder is used for the refractory lining which cannot endure even a small amount of calcium oxide (CaO).
  • Calcium oxide (CaO) is included in an amount less than 0.1 wt% in Alphabond 300 and in an amount of about 0.6 wt% in Alphabond 500, which are the products of Almatis. And, since it is included in an amount of about 3 wt% in castables, the calcium oxide (CaO) is present in the refractory as impurity levels.
  • fine particulate dead-burned magnesia is used instead of calcium aluminate cement to improve resistance to slag corrosion.
  • FIG. 1 shows a result of corrosion test for a refractory prepared by adding only an alumina binder to the refractory mixture composition D, using Usibelli slag with low viscosity under a reducing condition of 20% CO/N 2 at 1550 oC/4 hr. It can be seen that penetration hardly occurred. In contrast, complete penetration was observed for a refractory prepared by adding 3 wt% of alumina cement (Fig. 3). The penetration was about 2 mm for a refractory prepared by adding 3 wt% of alumina cement and 2 wt% of zircon (Fig. 2). This confirms that zircon greatly improves corrosion resistance.
  • the fine particulate powder is added to improve the flowability of the unshaped refractory.
  • the powder is sintered at heat treatment and thus improves strength.
  • ultrafine particulate ⁇ -alumina powder is used in an amount of 10 wt%.
  • the possibility of replacing the expensive ultrafine particulate alumina powder with cement was investigated.
  • the refractory composition B to which a small amount (3 ⁇ 5 wt%) of cement was added without the ultrafine particulate powder showed strength of about 25 MPa and density.
  • the composition M wherein only part of the ultrafine particulate powder was replaced with cement showed a high bending strength of about 40 MPa.
  • the addition amount of cement is specifically 5 wt% or less, more specifically 3 wt%.
  • PCE polycarboxylate ether
  • BASF VP65
  • alumina cement [3 wt% of cement comprising 0.6 wt% of calcium oxide (CaO)] can be used instead of the expensive ultrafine particulate alumina for a refractory which can endure a small amount of calcium oxide (CaO). And, it was also confirmed that, for a refractory which cannot endure even a small amount of calcium oxide (CaO), slag penetration can be greatly suppressed by adding a small amount of zircon.
  • composition of a cement comprising about 80 wt% of alumina used according to the present invention is described in Table 1, and the compositions of refractory mixtures according to the present invention are described in Table 2.
  • Composition (wt%) A B D M G Al 2 O 3 3-5 mm 7 7 0 0 15 SiC (average particle size) 0.3 ⁇ m 7.6 0 7.6 4 0 1.25 mm 38 38 45 40 30 750 ⁇ m 23 23 23 20 15 90 ⁇ m 3 3 3 10 7.4 20 ⁇ m 20 20 20 20 5 ⁇ m 1.4 1.4 1.4 6 5 Sum (%) 100 92.4 100 100 92.4 Boehmite (%) 0 0 3 3 3 3 3
  • the refractory mixture composition A was mixed with cement and zircon with various amounts, put in a 120 x ( ⁇ 15) x 20 mm stainless steel mold, and formed into an unshaped refractory by tapping on an electric vibration table. After drying at room temperature followed by drying at 60 oC and then at 100 oC for over 6 hours, respectively, the refractory was heated in the air at 5 oC/min to 1350 oC, kept at that temperature for 3 hours, and then cooled down at a rate of 5 oC/min. The sample was subjected to 3-point bending strength measurement with an outer span of 35 mm. Density was measured by the Archimedes’ method in boiling water. The characteristics of the refractories depending on the additives are shown in Table 3.
  • Table 3 shows the characteristics of the refractories prepared from the refractory mixture composition A.
  • 0Z0CA3B means 0 wt% of zircon/0 wt% of cement/3 wt% of alumina sol (10wt%).
  • Table 4 shows the characteristics of the refractories prepared from the refractory mixture composition B in the same manner as in Example 1.
  • 0Z0CA3B means 0 wt% zircon/0 wt% cement/3 wt% alumina sol (10wt%).
  • Table 5 shows the characteristics of the refractories prepared from the refractory mixture composition D in the same manner as in Example 1.
  • 0Z0CA3B means 0 wt% of zircon/0 wt% of cement/3 wt% of alumina sol (10wt%).
  • Table 6 shows the characteristics of the refractories prepared from the refractory mixture composition M in the same manner as in Example 1.
  • 0Z0CA3B means 0 wt% of zircon/0 wt% of cement/3 wt% of alumina sol (10wt%).
  • Table 7 shows the characteristics of the refractories prepared from the refractory mixture composition G in the same manner as in Example 1.
  • 0Z0CA3B means 0 wt% of zircon/0 wt% of cement/3 wt% of alumina sol (10wt%).
  • Slag corrosion test was performed using Usibelli slag under the condition of 20% CO/N 2 atmosphere at 1550 oC/4 hr.
  • a castable comprising the refractory mixture composition D as well as 2 wt% of zircon and 3 wt% of cement was formed into a shape of a cup with an outer diameter of 60 mm and an inner diameter of 30 mm.
  • heat treatment was performed as described in Example 1 to prepare a refractory sample D-4. After adding 35 g of slag powder over 2 hours while keeping temperature at 1550 oC and maintaining the temperature for additional 2 hours, the sample was furnace cooled and the cross-section of the sample was observed (Fig. 2).
  • a refractory sample D-2 was prepared in the same manner as Example 7 by adding only alumina sol without addition of zircon or cement to the refractory mixture composition D. Slag corrosion test result is shown in Fig. 1.
  • a refractory sample D-5 was prepared in the same manner as Example 7 by adding only 3 wt% of cement to the refractory mixture composition D. Slag corrosion test result is shown in Fig. 3.

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Abstract

L'invention concerne un matériau réfractaire non façonné contenant un mélange réfractaire d'alumine (Al2O3) et de carbure de silicium (SiC) auquel du ciment d'alumine, du zircon et un liant alumine sont ajoutés. Le matériau réfractaire présente une résistance élevée et une densité élevée ainsi qu'une résistance à la corrosion significativement améliorée, ce qui est dû à la réaction du zircon avec l'oxyde de calcium (CaO), diminuant fortement la corrosion par le laitier. L'utilisation du liant alumine assure un séchage rapide et une résistance suffisante pour la manipulation. Étant donné qu'un retrait ne se produit pratiquement pas après traitement thermique et qu'une faible porosité et une résistance élevée peuvent être obtenues, le matériau réfractaire convient très bien pour être utilisé, par exemple, en particulier, dans un gazéifieur.
PCT/KR2011/008188 2011-08-31 2011-10-31 Matériaux réfractaires non façonnés résistant à la corrosion à faible teneur en ciment WO2013032065A1 (fr)

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Cited By (1)

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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

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CN112851291A (zh) * 2021-03-05 2021-05-28 中冶武汉冶金建筑研究院有限公司 一种利用废弃碳化硅棚板的碳化硅质泥浆及其制备方法

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US2852401A (en) * 1955-06-13 1958-09-16 Harbison Walker Refractories Unshaped high temperature refractory
US5204298A (en) * 1990-11-28 1993-04-20 Harima Ceramic Co., Ltd. Basic monolithic refractories
US5972102A (en) * 1996-10-29 1999-10-26 North American Refractories Co. Hydraulically-bonded monolithic refractories containing a calcium oxide-free binder comprised of a hydratable alumina source and magnesium oxide
US20100093513A1 (en) * 2008-03-28 2010-04-15 Shigeru Nakama Refractory composition, formed refractory article, and sintered refractory article

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2852401A (en) * 1955-06-13 1958-09-16 Harbison Walker Refractories Unshaped high temperature refractory
US5204298A (en) * 1990-11-28 1993-04-20 Harima Ceramic Co., Ltd. Basic monolithic refractories
US5972102A (en) * 1996-10-29 1999-10-26 North American Refractories Co. Hydraulically-bonded monolithic refractories containing a calcium oxide-free binder comprised of a hydratable alumina source and magnesium oxide
US20100093513A1 (en) * 2008-03-28 2010-04-15 Shigeru Nakama Refractory composition, formed refractory article, and sintered refractory article

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
DE212016000023U1 (de) 2015-12-16 2017-06-08 Calderys France Giessbare feuerfeste Zusammensetzungen, umfassend Zeolithmikrostrukturen, und Verwendungen davon

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