KR100489196B1 - A method for preparing electro-fused Mg-Cr clinkers using refractory wastes - Google Patents

A method for preparing electro-fused Mg-Cr clinkers using refractory wastes Download PDF

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KR100489196B1
KR100489196B1 KR10-2000-0080327A KR20000080327A KR100489196B1 KR 100489196 B1 KR100489196 B1 KR 100489196B1 KR 20000080327 A KR20000080327 A KR 20000080327A KR 100489196 B1 KR100489196 B1 KR 100489196B1
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mag
cro
waste
molten
lead
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KR20020051006A (en
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전명철
김선욱
조용호
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주식회사 포스코
재단법인 포항산업과학연구원
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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
    • C04B35/04—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 based on magnesium oxide
    • C04B35/043—Refractories from grain sized mixtures
    • C04B35/047—Refractories from grain sized mixtures containing chromium oxide or chrome ore
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
    • 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
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653—Processes involving a melting step
    • C04B35/657—Processes involving a melting step for manufacturing refractories

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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)
  • Processing Of Solid Wastes (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

본 발명의 전융(electro-fused) 마그-크로 클링커를 제조하는 방법은 a) 마그-크로 폐연와(RDB-63F)를 선별 수집하여 불순물을 제거하는 단계; b) 상기 불순물이 제거된 마그-크로 폐연와를 적정 입도로 분쇄하는 단계; c) 상기 분쇄된 마그-크로 폐연와 분말을 아크전기로에 투입하여 고온에서 용융시키는 단계; 및 d) 상기 용융된 마그-크로 폐연와를 냉각시켜 전융 마그-크로 클링커를 제조하는 단계를 포함한다. Method for producing an electro-fused mag-clinker of the present invention comprises the steps of: a) collecting the Mag-Cro closed lead (RDB-63F) to remove impurities; b) pulverizing the mag-cro waste waste with the impurities removed to an appropriate particle size; c) injecting the pulverized mag-black waste lead and powder into an arc electric furnace and melting them at high temperature; And d) cooling the molten Mag-Cro closed lead to produce an molten Mag-Crolinker.

Description

마그-크로 폐연와를 재활용하여 전융 마그-크로 클링커를 제조하는 방법{A method for preparing electro-fused Mg-Cr clinkers using refractory wastes} A method for preparing electro-fused Mg-Cr clinkers using refractory wastes}

발명의 분야Field of invention

본 발명은 마그-크로(Mg-Cr) 폐연와의 재활용하여 전융(electro-fused) 마그-크로 클링커의 제조 방법에 관한 것으로, 보다 상세하게는 제철소에서 발생하는 RDB-63F 마그-크로 폐연와를 재활용하여 전융 마그-크로 클링커를 제조하는 방법에 관한 것이다. The present invention relates to a method for producing an electro-fused mag-clinker by recycling with Mg-Cr waste smoke, and more specifically, to recycling the RDB-63F Mag-Cro waste smoke produced in steel mills. The present invention relates to a method for producing a molten mag-clinker.

종래 기술Prior art

일반적으로 제철소 제강용 전기 정련로에서는 로내벽의 작업 내화물로서 마그-크로계 내화물(RDB-63F)이 많이 사용되고 있다. 이들 마그-크로계 내화물들은 가혹한 정련조업에 적합한 내열성과 내식성을 보유하고 있어 정련로용 내화물로서 널리 사용되고 있다. 그러나 사용 후 남는 마그-크로 폐연와는 크롬을 함유하고 있으며, 이들 크롬이 6가 크롬으로 발생될 가능성이 높아 후처리 방법에 있어 많은 어려움이 있다. In general, Mag-Cro-based refractory (RDB-63F) is frequently used as a working refractory material in the furnace wall in an electric refining furnace for steelworks steelmaking. These mag-chromic refractory materials are widely used as refractories for refining furnaces because they possess heat resistance and corrosion resistance suitable for harsh refining operations. However, the remaining mag-chrome waste smoke after use contains chromium, and since these chromium is likely to be generated as hexavalent chromium, there are many difficulties in the post-treatment method.

현재 마그-크로 폐연와의 적합한 재활용 방법의 부재로 인해 단순매립에만 의존하고 있는 실정이다. 향후 이러한 단순 매립은 매립지의 부족 및 환경오염 가능성으로 인해 점차 제약을 받는 추세이므로 보다 새로운 처리방법을 강구할 필요가 있으며, 더 나아가 이들 폐연와의 재활용에 대하여 집중적인 연구가 요청되고 있다. Currently, due to the lack of a suitable recycling method with Mag-Cro waste smoke, only the landfill is relied on. In the future, such simple landfills are increasingly restricted due to the lack of landfills and the possibility of environmental pollution. Therefore, it is necessary to devise new treatment methods, and further, intensive research on recycling with these waste smokes is required.

본 발명은 상기한 바와 같은 문제점을 해결하기 위한 것으로서, 지금까지 단순 매립되어온 RDB-63F 마그-크로 폐연와를 재활용하여 전융 마그-크로 클링커를 제조하는 방법을 제공하기 위한 것이다. The present invention is to solve the problems as described above, to provide a method for producing a molten mag-clinker by recycling the RDB-63F Mag-Cro closed waste that has been simply buried up to now.

상기한 본 발명의 목적을 달성하기 위하여, 본 발명은 In order to achieve the above object of the present invention, the present invention

a) 마그-크로 폐연와(RDB-63F)를 선별 수집하여 불순물을 제거하는 단계;a) screening and collecting the Mag-Cro closed lead (RDB-63F) to remove impurities;

b) 상기 불순물이 제거된 마그-크로 폐연와를 적정 입도로 분쇄하는 단계;b) pulverizing the mag-cro waste waste with the impurities removed to an appropriate particle size;

c) 상기 분쇄된 마그-크로 폐연와 분말을 아크전기로에 투입하여 고온에서 용융시키는 단계; 및 c) injecting the pulverized mag-black waste lead and powder into an arc electric furnace and melting them at high temperature; And

d) 상기 용융된 마그-크로 폐연와를 냉각시켜 전융 마그-크로 클링커를 제조하는 단계d) cooling the molten Mag-Cro closed lead to produce an molten Mag-Crolinker

를 포함하는 마그-크로 폐연와의 재활용하여 전융 마그-크로 클링커를 제조하는 방법을 제공한다.It provides a method for producing an electrolytic molten mag-clinker by recycling with a mag-black waste smoke comprising a.

이하, 본 발명을 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명의 전융 마그-크로 클링커의 제조 방법은The method for producing the molten mag-croclinker of the present invention

a) 마그-크로 폐연와(RDB-63F)를 선별 수집하여 불순물을 제거하는 단계;a) screening and collecting the Mag-Cro closed lead (RDB-63F) to remove impurities;

b) 상기 불순물이 제거된 마그-크로 폐연와를 적정 입도로 분쇄하는 단계;b) pulverizing the mag-cro waste waste with the impurities removed to an appropriate particle size;

c) 상기 분쇄된 마그-크로 폐연와 분말을 아크전기로에 투입하여 고온에서 용융시키는 단계; 및 c) injecting the pulverized mag-black waste lead and powder into an arc electric furnace and melting them at high temperature; And

d) 상기 용융된 마그-크로 폐연와를 냉각시켜 전융 마그-크로 클링커를 제조하는 단계를 포함한다.d) cooling the molten Mag-Cro closed lead to produce a molten Mag-Crolinker.

본 발명의 전융 마그-크로 클링커의 제조시 원료로 사용되는 RDB-63F 마그-크로 폐연와는 제철소의 정련로 수리시 방출되는 것을 분리 수집한 것이다. RDB-63F 마그-크로 폐연와는 마그네슘산화물(MgO) 30 내지 35 중량%와 크롬산화물(Cr2O3) 40 내지 50 중량%를 함유하는 폐연와를 의미한다. 분리 수집된 이들 RDB-63F 폐연와는 표면에 내화물 시공시 적용한 모르타르 및 기타 이물이 붙어 있고, 또한 가동면은 정련조업시 내화물에 침투한 금속 등이 들러 붙어 있으며, 고온 진공조업으로 크롬 성분 휘발로 인하여 부분적인 변색이 발생된 것이 대부분이다. 폐연와가 원료로서 가치를 지니기 위해서는 성분의 균일성이 요구되므로 가동면의 크롬 휘발로 인한 변색층을 물리적으로 제거하고 육안으로 식별되는 조대 금속 성분을 제거한다. 일차적으로 불순물 층을 제거해 준 폐연와는 고압의 수세를 이용하여 표면에 들러붙은 내화 모르타르 불순물을 제거해 주는 것이 바람직하다.RDB-63F Mag-Cro closed waste used as a raw material in the manufacture of the molten Mag-Crolinker of the present invention is collected separately from the release of the steel mill refinery. RDB-63F Mag-Cro closed lead refers to a closed lead containing 30 to 35% by weight of magnesium oxide (MgO) and 40 to 50% by weight of chromium oxide (Cr 2 O 3 ). These collected and separated RDB-63F waste smokes adhered to the surface with mortar and other foreign materials applied during refractory construction, and the movable surface contains metals penetrated into the refractory during refining operation. Most discoloration has occurred. In order for waste wastes to be valuable as raw materials, uniformity of the components is required, so that the discoloration layer due to the chromium volatilization on the movable surface is physically removed and the coarse metal component identified by the naked eye is removed. It is preferable to remove the refractory mortar impurities adhering to the surface by using high pressure washing with the waste smoke which first removed the impurity layer.

불순물을 제거한 마그-크로 폐연와를 적정 입도로 분쇄한다. 분쇄 작업은 죠크러셔 등을 이용하여 조분쇄할 수 있으며, 이에 한정되는 것은 아니다. 조분쇄한 폐연와의 입도는 20㎜ 이하인 것이 바림직하다. 본 발명에서는 이 조분쇄물에 자력선광을 적용하여 미세한 금속 불순물을 추가로 제거할 수 있다. 자력선광을 거친 분쇄물은 추가적인 분쇄공정을 통하여 전융조업에 적정한 입도로 재분쇄한 후 입도 선별한다. 이때 2차 분쇄된 폐연와 분말의 입도는 1∼10㎜의 범위에 있는 것이 바람직하다.Mug-free waste lead is removed to an appropriate particle size. The grinding operation may be coarsely pulverized using a jaw crusher, but is not limited thereto. The particle size of the coarsely ground waste smoke is preferably 20 mm or less. In the present invention, fine coarse impurities can be further removed by applying magnetic beneficiation to the coarse ground matter. Grinded products, which have undergone magnetic beneficiation, are regrind to a particle size suitable for the electrolytic operation through an additional grinding step and then the particle size is selected. At this time, the particle size of the secondary pulverized waste smoke and powder is preferably in the range of 1 to 10mm.

적정 입도로 분쇄된 마그-크로 폐연와 분말을 아크전기로에 투입하여 마그-크로 폐연를 초고온에서 용융시킨다. 아크전기로의 예로는 아크전융로(Arc Melting Furnace)가 있다. 용융 시간은 배치당 반응물의 양에 의존하나 통상 500kg의 원료를 전융하는 경우 용융시간은 4시간 이하로 하는 것이 바람직하다. 용융온도는 2000℃ 이상인 것이 바람직하다.Mag-cro waste smoke and powder ground to an appropriate particle size are introduced into an arc electric furnace to melt the mag-cro waste smoke at an extremely high temperature. An example of an arc furnace is the Arc Melting Furnace. Melting time depends on the amount of reactants per batch, but when melting 500 kg of raw material, the melting time is preferably 4 hours or less. It is preferable that melting temperature is 2000 degreeC or more.

상기 용융된 마그-크로 폐연와를 냉각시켜 전융 마그-크로 클링커를 제조한다. 냉각공정은 공기중에서 서서히 냉각시키는 것이 바람직하다. 냉각이 완료된 전융물을 물리적으로 적정 입도로 분쇄하면 크롬 함량이 25% 이상이고 평균 입자크기가 100㎛ 이상인 양질의 전융 마그-크로 클링커를 얻을 수 있다.The molten Mag-Cro closed waste is cooled to prepare an molten Mag-Crolinker. The cooling step is preferably cooled slowly in air. By physically grinding the cooled molten metal to an appropriate particle size, it is possible to obtain a high quality electrolytic mag-clinker having a chromium content of 25% or more and an average particle size of 100 µm or more.

이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나, 하기의 실시예는 본 발명의 이해를 돕기 위하여 제시되는 것일 뿐 본 발명이 하기하는 실시에에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are only presented to aid the understanding of the present invention, and the present invention is not limited to the following examples.

실시예 및 비교예Examples and Comparative Examples

실시예 1Example 1

먼저, 제철소의 정련로 수리시 방출되는 마그-크로 폐연와중 RDB-63F 연와를 분리 수집하였다. 분리 수집된 RDB-63F 폐연와의 표면에 붙어 있는 모르타르, 금속, 기타 이물질을 제거하였다. 일차적으로 불순물 층을 제거해 준 폐연와를 고압 수세하여 표면에 들러붙은 내화모르타르 불순물을 제거하였다. 수세를 거친 폐연와를 죠크러셔로 평균입도 20㎜ 이하가 되도록 1차 조분쇄하였다. 이 조분쇄물에 자력선광을 적용하여 미세한 금속 불순물을 추가로 제거하였다. 자력선광을 거친 분쇄물은 추가적인 분쇄공정을 통하여 평균입도 5㎜가 되도록 재분쇄한 후 입도 선별하였다. 분쇄된 폐연와 분말 400kg을 아크전융로에 투입하고 2000℃ 이상의 초고온에서 3시간 용융시켰다. 용융된 마그-크로 폐연와를 공기중에서 서서히 냉각시켜 전융 마그-크로 클링커를 제조하였다. 냉각이 완료된 전융물을 물리적으로 적정 입도로 분쇄하여 평균 입자크기가 100㎛ 이상이고 크롬함량이 25% 이상인 전융 마그-크로 클링커를 얻었다. First, the RDB-63F lead was separated and collected from the Mag-Cro closed lead released during repair of the steel mill. The mortar, metal, and other foreign matter adhering to the surface of the collected RDB-63F waste smoke were removed. The waste smoke, which first removed the impurity layer, was washed with high pressure to remove the refractory mortar impurities adhering to the surface. After washing with water, the spent soft pea was firstly pulverized with a jaw crusher to have an average particle size of 20 mm or less. Magnetic light beneficiation was applied to this coarse ground to further remove fine metallic impurities. Grinded product through magnetic beneficiation was regrind to an average particle size of 5 mm through an additional grinding process, and then the particle size was selected. 400 kg of the pulverized waste smoke and powder were put into an arc fusion furnace and melted at an ultra-high temperature of 2000 ° C. or higher for 3 hours. The molten Mag-Cro closed lead was slowly cooled in air to prepare a molten Mag-Crolinker. The cooled melt was physically ground to an appropriate particle size to obtain an electrolytic mag-clinker having an average particle size of 100 μm or more and a chromium content of 25% or more.

본 발명은 단순매립에 의하여 처리되어 온 마그-크로 폐연와를 재활용함으로써 매립지의 부족, 환경오염 등의 문제를 해결할 수 있다. 또한 본 발명의 마그-크로 폐연와의 전융공정 통하여 제조된 전융 마그-크로 클링커는 크롬 함량이 높아 내화물 원료로 사용될 수 있다. The present invention can solve problems such as lack of landfills, environmental pollution, etc. by recycling the waste-wax mag-chrome that has been treated by a simple landfill. In addition, the molten mag-clinker prepared through the melting process with the mug-chrom waste lead of the present invention can be used as a refractory raw material with high chromium content.

본 발명의 단순한 변형 또는 변경은 모두 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (1)

a) 마그-크로 폐연와(RDB-63F)를 선별 수집하여 불순물을 제거하는 단계;a) screening and collecting the Mag-Cro closed lead (RDB-63F) to remove impurities; b) 상기 불순물이 제거된 마그-크로 폐연와를 20 mm 이하의 입도로 분쇄하는 단계;b) pulverizing the impurities-removed mug-black waste smoke with a particle size of 20 mm or less; c) 상기 분쇄된 마그-크로 폐연와 분말을 아크전기로에 투입하여 2000℃ 이상의 온도에서 용융시키는 단계; 및 c) injecting the pulverized mag-black waste lead and powder into an arc electric furnace to melt at a temperature of 2000 ° C. or higher; And d) 상기 용융된 마그-크로 폐연와를 냉각시켜 전융 마그-크로 클링커를 제조하는 단계d) cooling the molten Mag-Cro closed lead to produce an molten Mag-Crolinker 를 포함하는 마그-크로 폐연와를 재활용하여 전융 마그-크로 클링커를 제조하는 방법. Method for producing a molten Mag-Crolinker by recycling the Mag-Cro closed waste containing.
KR10-2000-0080327A 2000-12-22 2000-12-22 A method for preparing electro-fused Mg-Cr clinkers using refractory wastes KR100489196B1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05339615A (en) * 1992-06-10 1993-12-21 Daido Steel Co Ltd Effective utilization method of waste brick for steel making
JPH07291718A (en) * 1994-04-15 1995-11-07 Nippon Steel Corp Magnesite-chrome refractory brick
KR19980051172A (en) * 1996-12-23 1998-09-15 김종진 Basic dry-ning fireproof composition with excellent corrosion resistance and adhesion
KR20000039555A (en) * 1998-12-14 2000-07-05 이구택 Ladle filling material for vacuum refining

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05339615A (en) * 1992-06-10 1993-12-21 Daido Steel Co Ltd Effective utilization method of waste brick for steel making
JPH07291718A (en) * 1994-04-15 1995-11-07 Nippon Steel Corp Magnesite-chrome refractory brick
KR19980051172A (en) * 1996-12-23 1998-09-15 김종진 Basic dry-ning fireproof composition with excellent corrosion resistance and adhesion
KR20000039555A (en) * 1998-12-14 2000-07-05 이구택 Ladle filling material for vacuum refining

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