KR920005403B1 - Preparing method of cao refractories - Google Patents
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- KR920005403B1 KR920005403B1 KR1019890020176A KR890020176A KR920005403B1 KR 920005403 B1 KR920005403 B1 KR 920005403B1 KR 1019890020176 A KR1019890020176 A KR 1019890020176A KR 890020176 A KR890020176 A KR 890020176A KR 920005403 B1 KR920005403 B1 KR 920005403B1
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- C—CHEMISTRY; METALLURGY
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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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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B35/03—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
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Abstract
Description
제1도는 본 발명에 따라 제조된 소성체의 전자현미경사진1 is an electron micrograph of a fired body produced according to the present invention
본 발명은 용융금속의 정련용 용기 또는 용융금속내에 존재하는 비금속금재물 제거용으로 사용되는 CaO 내화재를 제조하는 방법으로서, 보다 상세하게는 흡습억제효과가 우수한 CaO 내화제를 제조하는 방법에 관한 것이다.The present invention relates to a method for manufacturing a CaO refractory material used for refining a molten metal refining vessel or a non-metallic metal material present in the molten metal, and more particularly, to a method for producing a CaO refractory material having an excellent moisture absorption inhibitory effect. .
일반적으로 CaO는 용융금속내에 존재하는 불순원인 P,S 그리고 비금속개재물등의 제거에 매우 유효한 물질로 알려져 정련용 융제(flux)로서 널리 사용되어왔다. 뿐만아니라 정련반응의 효율성을 증가시키기 위해 CaO내화재를 용융금속의 정련용 용기(예, ladle)에 사용하려는 노력이 지속적으로 되어 오고 있다. 또한 최근에는 보다 적극적인 방법으로서 CaO내화재를 filter형상으로 제조하여 용강중 비금속 개재물을 저감하기 위한 방법(일명 filtration법)이 활발히 연구되고 있다. 즉, 용강중에 고체로 존재하는 알루미나 개재물을 CaO내화물과 접촉시켜 식(1)과 같은 반응에 의해 저융점의 복합산화물로 액화시키면 개재물 상호간의 응집이 용이해지므로 조대화되어 용강/개재물간의 비중차이에 의해 부상분리가 용이해진다.In general, CaO has been widely used as a flux for refining and is known as a very effective material for removing impurities such as P, S, and non-metallic inclusions present in molten metal. In addition, efforts have been made to use CaO refractories in molten metal refining vessels (eg ladles) to increase the efficiency of refining reactions. In recent years, as a more aggressive method, a method for reducing non-metallic inclusions in molten steel by preparing CaO refractory material in a filter form (aka filtration method) has been actively studied. In other words, when alumina inclusions present as solids in molten steel are contacted with CaO refractory to liquefy into composite oxides of low melting point by the reaction as shown in Eq. This makes the separation of flotation easier.
12CaO+Al2O3=12CaO.7Al2O3(1)12CaO + Al 2 O 3 = 12CaO.7Al 2 O 3 (1)
그런데 이러한 장점을 갖고 있는 CaO내화재는 현재까지 극히 제한적으로 사용되고 있으며 그 이유로서는 식(2)에 나타낸 바와 같이 CaO자체가 대기중의 수분과 반응하여 소석회(Ca(OH)2)를 생성하며 그 결과 부피팽창이 일어남에 따라 내화재로서의 사용이 불가능하고 또한 야금반응에 있어서도 CaO에 비해 불량하다.By the way, CaO refractory material having such an advantage is extremely limited until now, and the reason is that CaO itself reacts with moisture in the air to produce calcareous lime (Ca (OH) 2 ) as shown in Equation (2). As the volume expansion occurs, it cannot be used as a refractory material and is poor in comparison with CaO in the metallurgical reaction.
CaO+H2O=Ca(OH)2(2)CaO + H 2 O = Ca (OH) 2 (2)
일반적으로 내화물은 성형과 소성공정을 거쳐 제조되는데 CaO내화재의 경우 제조상의 문제점을 해결하기 위한 종래의 방법을 살펴보면 다음과 같다.In general, the refractory material is manufactured through a molding process and a firing process. In the case of a CaO refractory material, a conventional method for solving manufacturing problems is as follows.
첫째로, 보호피막법을 들 수 있는데, 이 방법은 성형과정중에 CaO자체의 소화성을 방지시키기 위한 것으로서 예를들면 CaO입자표면에 합성수지, 타르류등의 물리적 도포법과 CO2개스를 이용, 석회석피막을 형성하는 화학적인 도포법 그리고 금속성분을 진공증착시키는 방법등이 있다. 둘째로, 결정 성장법이 있는데, 이 방법은 CaO입자자체의 비표면적을 감소시켜 소화를 완화시키는 방법으로서, 이에 대한 예로는 CaO입자를 고온소성하거나 CaO 결정성장제인 Al2O3, Fe2O3, TiO2등의 성분을 가진 물질을 첨가하여 CaO입자를 성장시키는 방법 등이 있다.First, the protective coating method, which is to prevent CaO itself from extinguishing during the molding process, for example, using a physical coating method such as synthetic resin, tar, etc. on the surface of the CaO particles and using a CO 2 gas Chemical coating method for forming a metal and vacuum deposition of metal components. Secondly, there is a crystal growth method, which reduces the specific surface area of the CaO particles themselves to mitigate digestion. Examples of this method include the high temperature firing of CaO particles or Al 2 O 3 , Fe 2 O, which are CaO crystal growth agents. And a method of growing CaO particles by adding a substance having a component such as 3 or TiO 2 .
이와 같은 종래의 방법들을 살펴보면 주로 CaO내화재를 만들기 위해서 CaO원료에 대한 단순한 소화방지책에 지나지 않는다.Looking at such conventional methods, it is merely a simple anti-digestion measure for CaO raw materials in order to make CaO refractory material.
한편, 종래의 CaO내화재 제조에 있어서 소성 결합제(binder)로서는 크게 산화류와 염류로 구분되며, 산화류로서는 화학성분으로 볼때 Al2O3, Fe2O3, TiO2, SiO2, P2O5, Cr2O3등이 있으며, 염류로서는 CaCl2등이 있다.On the other hand, in the manufacture of conventional CaO refractory material as a plastic binder (binder) is largely divided into the oxidation and salts, and the oxidation type in terms of chemical components Al 2 O 3 , Fe 2 O 3 , TiO 2 , SiO 2 , P 2 O 5 , Cr 2 O 3, etc., and salts include CaCl 2 .
이와 같은 것들은 기본적으로 CaO와 저융점을 형성할 수 있는 것들로서 널리 보편화된 이론이지만, 실용성면에서 이들 성분을 함유한 물질에 대해서는 아직도 불명확하다.These are fundamentally widely accepted theories that can form CaO and low melting points, but are still unclear about materials containing these components in practical terms.
또한 Si-Oil을 이용한 CaO분말의 흡습을 억제하는 방법이 알려져 있는데, 이러한 방법으로서는 취입용 CaO계 flux에 있어서 취입성(injectabilty)확보를 위한 방법을 들 수 있으며 이 방법은 상온상태에서 CaO분말에 유기물질인 Si-Oil을 피복시킴으로써 대기와의 접촉을 막아 흡습억제에 의한 분말의 취입성확보에 지나지 않으며 CaO소성시와 같은 고온에서의 작용효과에 대해서는 아직 밝혀진 것이 없다.In addition, a method of suppressing moisture absorption of CaO powder using Si-Oil is known, and such a method may be a method for securing injection property in a CaO-based flux for blowing, which is applied to a CaO powder at room temperature. The coating of Si-Oil, which is an organic material, prevents contact with the atmosphere, thereby ensuring the blowing of powder by moisture absorption inhibition, and there is no known effect on the high temperature such as CaO firing.
따라서, 본 발명은 액체의 유기물질인 Si-Oil을 이용하여 CaO입자에 고르게 도포시켜 소성함으로써 원료상태 및 성형과정에서의 흡습억제는 물론 소성시 CaO입자에 피복된 Si-Oil이 대기중의 산소와 반응하여 SiO2화함에 따라 CaO입자의 전표면에 CaO-SiO2계 저융점 안정화합물층을 형성시켜 소결반응 촉진은 물론 완제품의 흡습억제 효과를 가져오는 CaO내화재를 제조하고자 하는데 그 목적이 있다.Therefore, in the present invention, Si-Oil, which is a liquid organic material, is evenly applied to CaO particles and calcined, thereby suppressing moisture absorption in the raw material state and the molding process as well as Si-Oil coated on CaO particles during firing. The purpose of the present invention is to produce a CaO refractory material that promotes sintering reaction and inhibits moisture absorption of the finished product by forming a CaO-SiO 2 based low melting point stable compound layer on the entire surface of the CaO particles by reacting with SiO 2 .
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 CaO에 바인더로서 Si-Oil용액을 CaO중량에 대하여 5-25%첨가하여 성형한 다음 1200-1350℃에서 소성하여 CaO내화제를 제조하는 방법에 관한 것으로서, 이를 보다 상세히 설명하면 다음과 같다.The present invention relates to a method of preparing CaO refractory by adding Si-Oil solution as a binder to CaO by adding 5-25% to CaO weight and then calcining at 1200-1350 ° C. same.
즉, 벤진등의 방향족 탄화수소계나 또는 트로클로로메탄과 같은 염화수소계용매에 CaO중량에 대하여 5-25중량%의 Si-Oil을 첨가하여 Si-Oil용액을 제조한 다음, 이 용액에 순수 CaO를 침적시켜 CaO입자에 상기 Si-Oil을 균일하게 도포시킨 후 대기 또는 150-200℃에서 상기 용매제를 제거시킨다.That is, a Si-Oil solution is prepared by adding 5-25% by weight of Si-Oil with respect to CaO weight to an aromatic hydrocarbon-based solvent such as benzine or a hydrogen chloride-based solvent such as trochloromethane, and then, pure CaO is deposited on the solution. The Si-Oil is uniformly applied to the CaO particles and then the solvent is removed at atmospheric or 150-200 ° C.
상기와 같이 용매제를 제거시킨 다음 통상의 방법으로 성형하고, 1200-1350℃에서 소성하므로서 본 발명에 부합되는 소성체(CaO내화재)가 제조된다.The solvent is removed as described above and then molded by a conventional method, and then fired at 1200-1350 ° C., thereby producing a fired body (CaO refractory material) conforming to the present invention.
상기 Si-Oil은 여러종류가 알려져 있는데, 특히 바람직한 것으로는 메틸-하이드로겐-폴리실록산을 들 수 있다.There are several known types of Si-Oil, and methyl-hydrogen-polysiloxane is particularly preferred.
이하, 실시예를 통하여 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail through examples.
[실시예 1]Example 1
벤젠등의 방향족 탄화수소계 용매나 트로클로로메탄과 같은 염화수소계 용매에 Si-Oil의 일종인 메틸-하이드로겐-폴리실록산을 CaO중량에 대하여 5-25중량%를 첨가하여 용액을 제조한 다음 100메쉬이하의 순수 CaO를 상기 용액에 침적한 후 습식혼합하여 180℃에서 용매제를 제거시켜 발명시료 A를 제조하고, 이에 대한 흡습정도를 순수 CaO와 함께 25℃에서 측정하고 그 결과를 하기 표 1에 나타내었다.5-25% by weight of methyl-hydrogen-polysiloxane, a kind of Si-Oil, was added to an aromatic hydrocarbon solvent such as benzene or a hydrogen chloride solvent such as chlorochloromethane to prepare a solution, and then 100 mesh or less. After dipping pure CaO in the solution and wet mixing to remove the solvent at 180 ℃ to prepare the invention sample A, the degree of hygroscopicity was measured at 25 ℃ with pure CaO and the results are shown in Table 1 below. It was.
[표 1]TABLE 1
상기 표 1에서 나타난 바와 같이, 발명시료(Si-Oil 순수 CaO)는 순수 CaO에 비하여 흡습속도가 현격히 완만함을 알 수 있다.As shown in Table 1, the invention sample (Si-Oil pure CaO) can be seen that the absorption rate is significantly slower than pure CaO.
상기 표 1의 발명시료와 SiO2분말을 순수 CaO와 혼합한 시료를 각각 500kg/cm2으로 가압하여 원통형태의 성형체를 제조한 다음 이 성형체를 하기 표 2와 같이 1200-1350℃의 대기저항로에서 소성하여 소성체를 제조하고 각 성형체에 대하여 25℃에서 시간에 따른 중량증가(%)(흡습성)를 측정하고 그 결과를 하기 표 2에 나타내었다.The invention sample of Table 1 and the sample mixed with pure CaO and SiO 2 powder were pressed at 500 kg / cm 2 , respectively, to prepare a molded article having a cylindrical shape, and then the molded article had an atmospheric resistance of 1200-1350 ° C. as shown in Table 2 below. By firing at to prepare a fired body, the weight increase (%) (hygroscopicity) with time at 25 ℃ for each molded body was measured and the results are shown in Table 2 below.
[표 2]TABLE 2
상기 표 2에 나타난 바와 같이, Si-Oil로 처리된 CaO소성체(발명체)가 순수 CaO+SiO2(종래체)에 비해 수화반응(CaO+H2O=Ca(OH)2)이 덜 일어남을 알 수 있으며, 이는, 발명체의 파단면에 대한 전자현미경사진을 나타내는 제1도에서 알 수 있는 바와 같이, CaO입자에 도포된 SiO-Oil의 Si-H결합이 승온되면서 대기중의 산소와 결합하여 SiO2화하고 이것이 CaO입자와 반응하여 입자표면에 흡습이 여려운 CaO-SiO2계 산화물층을 만들기 때문이며, 이 산화물층은 저융점의 복합 산화물층으로 순수 CaO입자간의 결합제로서 소성 Binder의 역할도 하고 있음을 알 수 있다.As shown in Table 2, the CaO plastic body (invented) treated with Si-Oil is less hydrated (CaO + H 2 O = Ca (OH) 2 ) than pure CaO + SiO 2 (conventional). As can be seen in Figure 1, which shows an electron micrograph of the fracture surface of the invention, the oxygen in the atmosphere as the Si-H bond of the SiO-Oil applied to the CaO particles is raised This is because it combines with SiO 2 and reacts with CaO particles to form CaO-SiO 2 -based oxide layer which is difficult to absorb moisture on the surface of the particle. This oxide layer is a low melting point composite oxide layer, which is a binder between pure CaO particles. It can also be seen that the role of.
또한, CaO+SiO2소성체에 비해 흡습이 덜 일어나는 이유는 고체의 SiO2분말을 혼합한 경우보다 액체의 Si-Oil을 혼합함으로서 개개의 CaO입자 전표면적에 고른 CaO-SiO2복합 산화물층을 형성하였기 때문으로 생각된다.In addition, less moisture absorption occurs than CaO + SiO 2 fired bodies because the CaO-SiO 2 composite oxide layer evenly mixed with the entire surface area of the CaO particles is mixed by mixing the liquid Si-Oil with the solid SiO 2 powder. It is considered to be formed.
상술한 바와 같이, 본 발명은 CaO에 성형 및 소성의 바인더로서 Si-Oil만을 첨가하여 CaO내화재를 제조하므로서, 제조공정을 단순화시킬 수 있을 뿐만아니라 흡습 억제효과가 뛰어나 제강공정등에 적용하여 용강의 청정성향상에 기여할 수 있는 CaO내화재 제조에 효과가 있는 것이다.As described above, the present invention is prepared by adding only Si-Oil as a binder for forming and firing to CaO to manufacture a CaO refractory material, which not only simplifies the manufacturing process but also has an excellent moisture absorption inhibiting effect, and thus is applied to steel making processes to maintain cleanliness of molten steel. It is effective in producing CaO refractory materials that can contribute to improvement.
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