KR100891861B1 - Ceramic fiber inclusion blast furnace taphole mix - Google Patents
Ceramic fiber inclusion blast furnace taphole mix Download PDFInfo
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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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
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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
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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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
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/74—Ceramic products containing macroscopic reinforcing agents containing shaped metallic materials
- C04B35/76—Fibres, filaments, whiskers, platelets, or the like
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
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- C04B2235/5216—Inorganic
- C04B2235/522—Oxidic
- C04B2235/5224—Alumina or aluminates
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Abstract
본 발명은 고로 출선구의 폐쇄에 사용되는 내화물에 관한 것으로, 그 목적은 용선 및 슬랙에 의한 고온강도 및 내침식성이 우수한 세라믹 화이바함유 고로 출선구 폐쇄용 내화물을 제공하는 것이다.
The present invention relates to a refractory used for closing the blast furnace outlet, the object is to provide a refractory for closing the blast furnace outlet containing ceramic fiber bar excellent in high temperature strength and corrosion resistance by molten iron and slack.
상기 목적을 달성하기 위한 본 발명은, 중량%로, 탄화규소: 12~22%, 알루미나질 화이바: 5~10%, 점토: 5~10%, 티타늄산화물: 4~8%, 토상흑연: 6~10%, 금속실리콘: 2~5%, 질화규소철: 4~9%, 나머지 전융질 알루미나 및 기타 불가피한 불순물로 조성되는 세라믹 화이바함유 고로 출선구 폐쇄용 내화물에 관한 것을 그 기술적 요지로 한다.
The present invention for achieving the above object, in weight percent, silicon carbide: 12-22%, alumina fiber: 5-10%, clay: 5-10%, titanium oxide: 4-8%, earth graphite: 6 It is technically related to the refractory for closing the exit of a ceramic fiber-containing blast furnace, composed of ~ 10%, metal silicon: 2-5%, iron nitride: 4-9%, and the remaining electrolytic alumina and other unavoidable impurities.
고로 출선구, 고온강도, 내침식성, 세라믹 화이바, 티타늄산화물Blast furnace outlet, high temperature strength, corrosion resistance, ceramic fiber, titanium oxide
Description
본 발명은 고로 출선구의 폐쇄에 사용되는 내화물에 관한 것으로, 보다 상세하게는 고온강도 및 내침식성이 우수한 세라믹 화이바함유 고로 출선구 폐쇄용 내화물에 관한 것이다.
The present invention relates to a refractory used for closing the blast furnace outlet, and more particularly to a refractory for closing the ceramic fiber bar-containing blast furnace exit excellent in high temperature strength and corrosion resistance.
최근 대형고로의 출현으로 고온, 고압하에서 출선량, 출선회수가 증가되고 있는 추세이다. 이에 고로의 노황유지 및 출선작업부하 저감을 위한 대책으로 장시간의 출선에 견딜 수 있는 고온강도 및 내침식성이 우수한 내화물이 요구되고 있다.
With the emergence of large-scale blast furnaces, the amount of turnout and the number of turnouts are increasing under high temperature and high pressure. Accordingly, as a countermeasure for maintaining blast furnace rust and reducing work loads, a refractory having excellent high temperature strength and erosion resistance that can withstand long run times is required.
고로 출선구 폐쇄용 내화물에 관한 종래의 기술들 중에서 일본 공개특허공보 평12-247755호는 탄소재료를 주원료로 하고 알루미나 초미분, 금속알루미늄, 페로실리콘 단독 또는 혼합한 것에 유기결합재를 첨가하여 구성되는 고로 출선구 폐쇄 용 내화물에 관한 것이다. 이 내화물은 열간강도를 높여서 슬랙에 대한 내침식성을 향상시켜 장시간의 출선이 가능케 함과 동시에 충진시의 작업성 및 출선시의 개공성 향상을 목적으로 한 것이다. Japanese Patent Laid-Open Publication No. Hei 12-247755 has a carbon material as a main raw material, and is composed of an organic binder added to alumina ultrafine powder, aluminum metal, ferrosilicon alone, or a mixture thereof. It is about the refractory for closure of the blast furnace exit. This refractory is intended to improve the erosion resistance of the slag by increasing the hot strength to enable long-term outboarding, and to improve the workability during filling and openability during outboarding.
또한, 일본 공개특허공보 평11-1374호는 내화골재, 탄소질원료, 내화점토 및 바인더를 배합하여 이루어지는 출선구용 머드재료이며, 상기 바인더가 석탄입자, 아민류 등과 같은 유기용제 및 타르증류물을 함유하여 조기강도 및 내식성 향상을 목적으로 한 것이다.
In addition, Japanese Patent Laid-Open No. 11-1374 is a mud material for a tap opening formed by blending refractory aggregate, carbonaceous raw material, refractory clay, and a binder, and the binder contains organic solvents such as coal particles, amines, and tar distillates. The purpose is to improve early strength and corrosion resistance.
상기 종래기술들은 출선구 폐쇄용 내화물의 슬랙에 대한 고온강도 및 내침식성 향상을 목적으로 하고 있으나, 출선 말기에 슬랙에 의해 출선구 확대등 내침식성에 문제점이 있다.
The prior arts aim to improve the high temperature strength and erosion resistance of the slag of the refractory for closing the exit opening, but there is a problem in the erosion resistance such as expansion of the exit opening by the slack at the end of the departure.
본 발명은 이러한 문제를 해결하기 위한 것으로, 출선구 폐쇄용 내화물에 인성과 통기성을 높여주기 위한 알루미나성분의 세라믹 화이바를 첨가하여 휘발성분의 휘발에 의해 발생하는 균열을 억제함과 동시에 티타늄산화물을 사용하여 내화물의 열간강도를 높여 고온강도 및 내침식성이 우수한 고로 출선구 폐쇄용 내화물을 제공하는데, 그 목적이 있다.
The present invention is to solve this problem, by adding alumina-based ceramic fiber to increase toughness and breathability to the exit closure refractory to suppress cracks caused by volatilization of volatile components and at the same time use titanium oxide Therefore, to increase the hot strength of the refractory to provide a refractory for closing the blast furnace exit excellent in high temperature strength and corrosion resistance, the purpose is.
상기 목적을 달성하기 위한 본 발명의 고로출선구 폐쇄용 내화물은, 중량%로 탄화규소: 12~22%, 알루미나질 화이바: 5~10%, 점토: 5~10%, 티타늄산화물: 4~8%, 토상흑연: 6~10%, 금속실리콘: 2~5%, 질화규소철: 4~9%, 나머지 전융질 알루미나 및 기타 불가피한 불순물로 조성된다.
Refractory for closing the blast furnace outlet of the present invention for achieving the above object, by weight% silicon carbide: 12-22%, alumina fiber: 5-10%, clay: 5-10%, titanium oxide: 4-8 %, Earth graphite: 6-10%, metal silicon: 2-5%, iron nitride: 4-9%, the remaining electrolytic alumina and other unavoidable impurities.
이하, 본 발명을 보다 상세히 설명한다.
Hereinafter, the present invention will be described in more detail.
탄화규소: 12~22중량%Silicon Carbide: 12-22 wt%
내화물중 탄화규소는 슬랙에 대한 내침식성을 높이고 탄소의 산화방지에 효과적인 재료이다. 탄화규소의 함량이 12중량%미만이면 슬랙에 대한 내침식성이 불량하고 탄화규소의 산화에 의하여 생성되는 산화규소의 생성량이 적어 산화억제효과가 저하된다. 또한, 그 함량이 22중량%를 초과하면 탄화규소가 자체소결성이 없기 때문에 강도를 저하시키게 되므로, 그 함량을 12~22중량%로 제한하는 것이 바람직하다.
Silicon carbide in the refractory is an effective material for enhancing corrosion resistance to slack and preventing oxidation of carbon. If the content of silicon carbide is less than 12% by weight, corrosion resistance to slack is poor, and the amount of silicon oxide produced by oxidation of silicon carbide is small, so the oxidation inhibitory effect is lowered. In addition, if the content exceeds 22% by weight, silicon carbide is not self-sintering, so the strength is lowered, it is preferable to limit the content to 12 to 22% by weight.
알루미나질 화이바: 5~10중량%Alumina Fiber: 5 ~ 10 wt%
내화물중 알루미나질 화이바(fiber)는 폐쇄용 내화물의 인성과 통기성을 높이는 역할을 한다. 알루미나질 화이바는 알루미나(Al2O3)와 실리카(SiO2)성분으로 구성된다. 상기 알루미나질 화이바 함량이 5중량% 미만이면 폐쇄용 내화물의 인성증 진에 효과가 적으며, 함량이 10중량% 초과이면 강도가 저하되고 침식이 심하게 발생하므로, 그 함량을 5~10중량%로 제한하는 것이 바람직하다. The alumina fiber in the refractory serves to increase the toughness and breathability of the closing refractory. Alumina fiber is composed of alumina (Al 2 O 3 ) and silica (SiO 2 ) components. If the alumina fiber content is less than 5% by weight is less effective to increase the toughness of the refractories for closure, if the content is more than 10% by weight because the strength is lowered and erosion occurs badly, the content is 5 to 10% by weight It is desirable to limit.
상기 알루미나질 화이바는 사용온도에 따라서 고온형과 저온형으로 나뉜다. 고온형 화이바는 알루미나(Al2O3)의 함량이 높은 것이고, 저온형 화이바는 실리카(SiO2)의 함량이 높은 것인데, 본 발명의 실시예에서와 같이 사용부위의 온도가 높지않을 때에는 저온형 화이바를 사용하는 것이 바람직하다. The alumina fiber is divided into high temperature type and low temperature type according to the use temperature. High temperature fiber is a high content of alumina (Al 2 O 3 ), low temperature fiber is a high content of silica (SiO 2 ), as in the embodiment of the present invention when the temperature of the use site is not high temperature type It is preferable to use fiber.
또한, 상기 저온형 화이바(알루미나 함량이 40중량%이하)는 1~5mm로 절단하여 사용하는 것이 가장 바람직한데, 그 이유는 화이바의 길이가 1mm미만이면 길이가 짧아서 인성증진 효과가 적고, 5mm를 초과하면 혼련시 화이바 자체가 서로 얽혀서 화이바 첨가효과가 떨어지기 때문이다.
In addition, the low-temperature fiber (alumina content is less than 40% by weight) is most preferably used by cutting to 1 ~ 5mm, the reason is that if the length of the fiber is less than 1mm, the length is short, the toughness enhancing effect is less, 5mm If it exceeds, the fiber bar itself is entangled with each other when kneading, which decreases the effect of adding fiber bars.
점토: 5~10중량%Clay: 5-10 wt%
내화물중 점토는 가소성을 부여하기 위하여 사용된다. 그 함량이 5중량%미만이면 가소성부족으로 작업성이 떨어지며, 충진시 균열이 생겨 용선 및 슬랙의 침투로 개공성 불량이 될 뿐만 아니라 심도저하의 원인이 된다. 또한, 사용량이 10중량%초과이면 슬랙과 반응하여 저융물을 다량 생성하여 출선말기에 출선구경 확대를 초래하므로, 그 함량을 5~10중량%로 제한하는 것이 바람직하다.
Clays in refractory materials are used to impart plasticity. If the content is less than 5% by weight, the workability is reduced due to the lack of plasticity, and cracks are generated during filling, which leads to poor porosity due to penetration of molten iron and slack, and also causes a decrease in depth. In addition, when the amount of use exceeds 10% by weight, it is preferable to limit the content to 5 to 10% by weight because it reacts with the slack to produce a large amount of low melt, which leads to the expansion of the tap diameter at the end of the tap.
티타늄산화물(TiO2): 4~8중량% Titanium Oxide (TiO 2 ): 4 ~ 8 wt%
내화물중 티타늄산화물(TiO2)은 폐쇄용 내화물의 소결을 촉진시켜 고온에서의 열간강도를 높이는 역할을 한다. 티타늄산화물의 함량이 4중량%미만이면 열간강도를 충분히 높이지 못하고, 함량이 8중량%초과이면 과소결로 인한 수축이 심하여 사용하기에 적합하지 못하므로, 그 함량을 4~8중량%로 제한하는 것이 바람직하다.
Titanium oxide (TiO 2 ) in the refractory serves to increase the hot strength at high temperature by promoting the sintering of the closing refractory. If the content of titanium oxide is less than 4% by weight, the hot strength is not sufficiently increased. If the content of the titanium oxide is more than 8% by weight, the shrinkage due to over sintering is not suitable for use. Therefore, the content is limited to 4 to 8% by weight. It is preferable.
토상흑연: 6~10중량%Soil graphite: 6 ~ 10 wt%
내화물중 토상흑연은 폐쇄용 내화물의 슬랙에 대한 내침식성을 높이는 역할을 한다. 흑연에는 인상흑연과 토상흑연이 있다. 인상흑연은 흑연의 표면이 광택에 있고 매끈하여 다량 첨가시에는 혼련이 잘 되지않아 작업성을 저하시키므로, 본 발명에서는 토상흑연을 사용한다. 그 함량이 6중량%미만이면 슬랙에 대한 내침식성이 저하하고, 함량이 10중량%초과이면 토상흑연에 다량 함유되어 있는 불순물의 영향으로 내침식성이 저하하므로, 그 함량을 6~10중량%로 제한하는 것이 바람직하다.
Soil graphite in the refractory acts to increase the corrosion resistance to the slag of the refractory for the closure. Graphite has impression graphite and soil graphite. Impression graphite has the surface of graphite is smooth and smooth, and when a large amount is added, kneading is not performed well, and workability is reduced, therefore, earth graphite is used in the present invention. If the content is less than 6% by weight, the erosion resistance to slack is lowered. If the content is more than 10% by weight, the erosion resistance is reduced due to the impurities contained in the large amount of soil graphite, so the content is reduced to 6 to 10% by weight. It is desirable to limit.
금속실리콘: 2~5중량%, 질화규소철: 4~9중량%Metal silicon: 2 to 5 wt%, silicon nitride: 4 to 9 wt%
내화물중 금속실리콘과 질화규소철은 고온에서 소결을 촉진하여 고온강도를 높이는 작용을 하며, 단독으로 사용하기 보다는 동시에 사용하는 것이 효과적이다. 금속실리콘과 질화규소철은 각각의 함량이 2중량%미만과 4중량%미만이면 소결촉진효과가 작아 고온강도를 크게 높일 수 없으며, 각각의 함량이 5중량% 초과와 9중량% 초과이면 강도증진효과는 있으나 과소결로 조직이 치밀하게되어 개공성이 불량하게 되므로, 그 각각의 함량을 2~5중량%, 4~9중량%로 제한하는 것이 바람직하다.
Metallic silicon and silicon nitride in the refractory promote the sintering at high temperature to increase the high temperature strength, and it is more effective to use it simultaneously rather than alone. If the content of metal silicon and silicon nitride is less than 2% by weight and less than 4% by weight, the sintering promotion effect is small and the high temperature strength can not be greatly increased.If the content is more than 5% by weight and 9% by weight, the strength increase effect is increased. There is, but the oversintered structure becomes dense and poor porosity, it is preferable to limit the respective content of 2 to 5% by weight, 4 to 9% by weight.
내화물중 알루미나는 전융질알루미나, 소결알루미나 등과 같은 고순도의 인공 합성원료와 천연의 보오크사이트(Bauxite) 등이 사용된다. 이중에서 전융질알루미나가 결정입자가 조대하여 내침식성이 우수하므로, 본 발명에서는 전융질알루미나를 사용한다. As the alumina in the refractory, high purity artificial synthetic raw materials such as allothermal alumina, sintered alumina and the like and natural bauxite are used. In the present invention, the electrolytic alumina is coarse in crystal grains and excellent in corrosion resistance. Therefore, the present invention uses an electrolytic alumina.
전융질알루미나는 내침식성 및 소결성을 높이는 작용을 하며, 다른 성분들과의 합이 100중량%가 되도록 첨가되는데, 가장 바람직하게는 40중량% 이상 혼합한다.
The pre-aluminum alumina acts to increase the erosion resistance and sintering resistance, and is added so that the sum with other components is 100% by weight, most preferably 40% by weight or more.
본 발명의 내화물은 출선구 폐쇄재(머드재)로 이용된다. 내화물로 출선구를 폐쇄할때에는 머드건(mud gun)에 의해 충진된다. 내화물을 머드재로 사용할 때, 결합재로는 주로 타르가 이용되며, 통상 외삽으로 15~17중량%를 첨가한다. 본 발명에서도 통상의 방법에 따라 타르를 결합재로 사용한다.
The refractory material of the present invention is used as the exit closure material (mud material). When the exit is closed with refractory, it is filled by a mud gun. When using a refractory material as a mud material, tar is mainly used as a binder, and 15 to 17 weight% is normally added by extrapolation. In the present invention, tar is used as a binder according to a conventional method.
이하, 본 발명을 실시예를 통하여 보다 구체적으로 설명한다.
Hereinafter, the present invention will be described in more detail with reference to Examples.
[실시예]EXAMPLE
하기 표 1과 같은 조성비를 가진 고로 출선구 폐쇄용 내화물의 조성물에 15 중량%의 타르를 외삽으로 가해 60℃로 가온하면서 가압혼련한다. 상기 혼련된 것을 40x40x160mm의 크기로 성형하여 12시간 자연양생한 후, 선변화율, 곡강도, 내침식성 및 개공성을 평가하고 그 결과를 하기 표 1에 나타내었다.
15 weight percent tar is extrapolated to the composition of the blast furnace closure closing refractory having a composition ratio as shown in Table 1, followed by pressure kneading while heating to 60 ℃. After the kneaded material was molded to a size of 40x40x160mm and cured for 12 hours, the rate of change, bending strength, erosion resistance and porosity were evaluated, and the results are shown in Table 1 below.
300℃ 및 1500℃에서 선변화율과 곡강도를 측정하고, 내침식성은 고주파 유도용해로에서 고로 슬랙을 사용하여 1550℃에서 1시간 유지한 후 출선하여 시편의 잔존두께를 측정한다. 개공성은 시편제조용 굴삭기(core boring machine)를 이용하여 일정한 시간에 굴삭되는 깊이를 측정하여 판단한다.
The rate of change and the bending strength were measured at 300 ℃ and 1500 ℃, and the erosion resistance was maintained at 1550 ℃ for 1 hour using blast furnace slag in a high frequency induction furnace to measure the remaining thickness of the specimen. Openness is determined by measuring the depth to be excavated at a certain time using a core boring machine.
표 1에서 알 수 있는 바와 같이, 본 발명의 범위를 만족하는 발명예(1-5)는 비교예(1-5) 및 종래재와 비교하여 선변화율이 비교적 작고, 곡강도가 크며 내침식성과 개공성이 우수함을 알 수 있다.
As can be seen from Table 1, Inventive Example (1-5), which satisfies the scope of the present invention, has a relatively small linear change rate, a large bending strength, erosion resistance and development compared with Comparative Example (1-5) and conventional materials. It can be seen that the porosity is excellent.
상기한 바와 같이, 본 발명은 고로 출선구 폐쇄용 내화물의 고온강도 및 내침식성을 향상시켜 출선시간 연장 및 출선회수 저감등에 유용한 효과가 있다.As described above, the present invention improves the high temperature strength and erosion resistance of the blast furnace closure refractories has an effect useful for extending the departure time and reducing the number of times.
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| CN109575443A (en) * | 2018-12-24 | 2019-04-05 | 中国地质大学（北京） | A kind of graphite tailing composite material and preparation method |
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| CN1301934C (en) * | 2004-11-01 | 2007-02-28 | 武汉科技大学 | Briquette for iron-smelting blast furnace lining and its preparation method |
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| JPH0920551A (en) * | 1995-07-06 | 1997-01-21 | Kyushu Refract Co Ltd | Magnesia refractory mixed with calcia/titania-based compound oxide |
| JPH111374A (en) * | 1997-06-11 | 1999-01-06 | Nkk Corp | Mad material for tap hole |
| KR20000051478A (en) * | 1999-01-22 | 2000-08-16 | 구자홍 | Driving IC of Plasma Display Panel |
| JP2000247755A (en) * | 1999-02-23 | 2000-09-12 | Kurosaki Harima Corp | Carbonaceous filler for closing tap hole of blast furnace |
| KR20020050453A (en) * | 2000-12-21 | 2002-06-27 | 이구택 | Tap hole mix for blast furnace |
| JP6047504B2 (en) * | 2011-02-11 | 2016-12-21 | イシダ ヨーロッパ リミテッドＩｓｈｉｄａ Ｅｕｒｏｐｅ Ｌｉｍｉｔｅｄ | Container sealing device |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0920551A (en) * | 1995-07-06 | 1997-01-21 | Kyushu Refract Co Ltd | Magnesia refractory mixed with calcia/titania-based compound oxide |
| JPH111374A (en) * | 1997-06-11 | 1999-01-06 | Nkk Corp | Mad material for tap hole |
| KR20000051478A (en) * | 1999-01-22 | 2000-08-16 | 구자홍 | Driving IC of Plasma Display Panel |
| JP2000247755A (en) * | 1999-02-23 | 2000-09-12 | Kurosaki Harima Corp | Carbonaceous filler for closing tap hole of blast furnace |
| KR20020050453A (en) * | 2000-12-21 | 2002-06-27 | 이구택 | Tap hole mix for blast furnace |
| JP6047504B2 (en) * | 2011-02-11 | 2016-12-21 | イシダ ヨーロッパ リミテッドＩｓｈｉｄａ Ｅｕｒｏｐｅ Ｌｉｍｉｔｅｄ | Container sealing device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109575443A (en) * | 2018-12-24 | 2019-04-05 | 中国地质大学（北京） | A kind of graphite tailing composite material and preparation method |
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