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WO2014069751A1 - Ciment alumineux utilisant du laitier en fusion de haut-fourneau et du laitier de poche haute température, et son procédé de fabrication - Google Patents

Ciment alumineux utilisant du laitier en fusion de haut-fourneau et du laitier de poche haute température, et son procédé de fabrication Download PDF

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Publication number
WO2014069751A1
WO2014069751A1 PCT/KR2013/006680 KR2013006680W WO2014069751A1 WO 2014069751 A1 WO2014069751 A1 WO 2014069751A1 KR 2013006680 W KR2013006680 W KR 2013006680W WO 2014069751 A1 WO2014069751 A1 WO 2014069751A1
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WIPO (PCT)
Prior art keywords
slag
blast furnace
alumina cement
furnace slag
raw material
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Ceased
Application number
PCT/KR2013/006680
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English (en)
Korean (ko)
Inventor
정용수
김형석
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Research Institute of Industrial Science and Technology RIST
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Research Institute of Industrial Science and Technology RIST
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Publication of WO2014069751A1 publication Critical patent/WO2014069751A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/32—Aluminous cements
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
    • C04B7/44—Burning; Melting
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/06—Aluminous cements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Definitions

  • the present invention relates to alumina cement using molten blast furnace slag and hot ladle slag and a method of manufacturing the same.
  • Alumina cement contains 35 ⁇ 77% of Al 2 O 3 , and the main compounds are C 12 A 7 , CA, and CA 2 , and are classified into 1 to 5 alumina cements according to the Al 2 O 3 content.
  • alumina cement mixes limestone as CaO source and bauxite (Al (OH) 3 ) as Al 2 O 3 source, heats (melts, calcinates) and reacts at high temperature to make clinker once, It is pulverized and manufactured as a product.
  • various furnaces such as an electric furnace, a furnace, a blast furnace, a rotary kiln, a converter, and a tunnel kiln, are used.
  • Alumina cement has much faster strength than conventional Portland cement, and after 6 ⁇ 12 hours of mixing with water, it shows the strength after 28 days of Portland cement. In spite of the rapid strength development, the setting time is almost the same as that of Portland cement. Due to these excellent properties, the demand for use in civil engineering and construction sites is increasing, but the price of the alumina cement is 5 ⁇ 10 times higher than that of Portland cement because alumina cement uses electric energy for melting raw materials and bauxite. This product is expensive, so its use is limited. Accordingly, in order to reduce the manufacturing cost of alumina cement, there is an urgent need for a technology for developing an inexpensive bauxite alternative or reducing the use of electric energy.
  • the present invention is to provide alumina cement using a molten blast furnace slag and high temperature ladle slag that can significantly reduce the manufacturing cost by using the steel industry by-products and a method of manufacturing the same.
  • One embodiment of the present invention provides an alumina cement comprising blast furnace slag: 2-50 wt%, ladle slag: 1-5 wt%, limestone: 27 wt% or less and bauxite: 45-80 wt%.
  • Another embodiment of the present invention is to supply a raw material comprising molten blast furnace slag: 2-50% by weight, ladle slag: 1-5%, limestone: 27% by weight or less bauxite: 45-80% by weight to the electric furnace step; Melting the raw material by energizing three electrode rods provided in the electric furnace; Agitating the fused raw material by energizing two electrodes of the three electrodes; And it provides a method for producing alumina cement comprising the step of cooling the stirred raw material from the electric furnace after cooling.
  • the use of molten blast furnace slag and high temperature ladle slag as a substitute for the alumina cement raw material can reduce the use of expensive raw materials and reduce the production cost by reducing the use of electric energy by using sensible heat of the material. Cement and its manufacturing method can be provided.
  • the inventors of the present invention can reduce the use of alumina cement raw materials by using molten blast furnace slag and hot ladle slag, which are byproducts of the steel industry, as substitutes for alumina cement raw materials.
  • the present invention has been completed by recognizing that it is possible to effectively reduce the production cost of alumina cement by using the sensible heat of the molten blast furnace slag and the hot ladle slag to reduce the electrical energy used in the production of alumina cement.
  • the present invention provides alumina cement comprising blast furnace slag: 2 to 50% by weight, ladle slag: 1 to 5% by weight, limestone: 27% by weight or less and bauxite: 45 to 80% by weight. do.
  • blast furnace slag 2 to 50% by weight
  • ladle slag 1 to 5% by weight
  • limestone 27% by weight or less
  • bauxite 45 to 80% by weight. do.
  • Table 1 below shows examples of blast furnace slag, ladle slag and alumina cement main chemical components.
  • the alumina cement chemistry is specified in KS standards, and the description of chemical constituents that are not important or have impurities is excluded.
  • the blast furnace slag contains a large amount of CaO and shows that it can be used as a substitute for CaO raw materials required for alumina cement.
  • the blast furnace slag contains a small amount of Al 2 O 3 but also has a replacement effect of the bauxite in part.
  • Ladle slag can be classified into two types, silicon deoxidation slag, and A type aluminum deoxidation slag.
  • ladle slag also contains a large amount of CaO, and in the case of Class B, it contains a large amount of Al 2 O 3 .
  • the use of ladle slag, especially in the case of class B shows that it is possible to replace the expensive bauxite which is a raw material used to provide Al 2 O 3 when manufacturing alumina cement.
  • the ladle slag Fe 2 O 3 addition it serves to contain a certain amount, replacing the Fe 2 O 3 required for the alumina cement manufacture can also be carried out.
  • alumina cements are varied from one to five, each having a different component range. That is, the blast furnace slag and ladle slag is used as a substitute for the alumina cement raw material, wherein the alumina cement is blast furnace slag: 2 to 50% by weight, ladle slag: 1 to 5% by weight, limestone: 27% by weight or less and bake Site:
  • a variety of alumina cements can be provided from 1 to 5 by controlling to contain 45 to 80% by weight. Through this, it is possible to express the effect of reducing the raw material cost compared to the existing alumina cement.
  • the blast furnace slag is preferably included 2% by weight or more in order to increase the replacement effect of the limestone input for the provision of CaO and thereby reduce the raw material cost.
  • the blast furnace slag is injected into a molten state of high temperature during the production of alumina cement, it is preferable that the blast furnace slag is included as much as possible in order to make maximum use of the sensible heat (energy) of the blast furnace slag.
  • the content of the blast furnace slag exceeds 50% by weight, the CaO or Al 2 O 3 content of the alumina cement produced by the increase of the SiO 2 component is relatively low, thereby satisfying the composition required for the alumina cement It is difficult to make.
  • the content of the ladle slag is less than 1% by weight, there is a lack of replacement effect of the bauxite introduced to provide Al 2 O 3 . Since the ladle slag contains a large amount of Al 2 O 3 , it is preferable to use as much amount as possible for the replacement of bauxite. In addition, since the ladle slag is also a high temperature state in the manufacture of alumina cement, it is preferable to include a large amount in order to increase the energy saving effect by using sensible heat.
  • the content of the ladle slag exceeds 5% by weight has a disadvantage in that it is difficult to meet the composition required for the alumina cement, the content of the ladle slag is preferably in the range of 1 to 5% by weight.
  • the limestone is a raw material for providing CaO required for alumina cement.
  • the blast furnace slag and the ladle slag as a means for replacing the limestone as much as possible, but since the blast furnace slag and the ladle slag alone do not satisfy the CaO content required for the alumina cement, the alumina provided by the present invention is provided.
  • the cement may further comprise limestone.
  • the limestone is preferably in the range of 27% by weight or less, if it exceeds 27%, the effect of reducing the raw material and the manufacturing cost through which the present invention is to be lowered.
  • the blast furnace slag and the ladle slag alone can sufficiently provide CaO, in which case it may not include limestone.
  • the bauxite is a raw material for providing Al 2 O 3 required for alumina cement.
  • the present invention preferably utilizes the ladle slag to replace the bauxite, but the ladle slag alone does not satisfy the Al 2 O 3 content required for the alumina cement. Therefore, it is preferable that the alumina cement provided by this invention contains the said bauxite.
  • the bauxite is preferably in the range of 45 to 80% by weight, if less than 45% by weight it is difficult to provide enough Al 2 O 3 required for the production of alumina cement, when the present invention exceeds 80% by weight The reduction of raw materials to be obtained and the reduction of manufacturing cost through the same are lowered.
  • the alumina cement of the present invention provided as described above can reduce the use of expensive limestone and bauxite, thereby reducing the raw material cost by 20 to 40%, and increasing the utilization of steel by-products classified as industrial waste.
  • the alumina cement of the present invention includes both clinker in the form of agglomerates and cement obtained by pulverizing the clinker.
  • those of ordinary skill in the art will be able to manufacture a variety of alumina cements from 1 type to 5 types without repeated experiments or other difficulties with reference to the composition of Table 1 within the content range of the components provided by the present invention. Can be.
  • the present invention supplies a raw material containing molten blast furnace slag: 2 to 50% by weight, ladle slag: 1 to 5% by weight, limestone: 27% by weight or less and bauxite: 45 to 80% by weight. Doing; Melting all of the raw materials by energizing all three electrode rods provided in the electric furnace; Agitating the fused raw material by energizing two electrodes of the three electrodes; And it provides a method for producing alumina cement comprising the step of cooling the stirred raw material from the electric furnace after cooling.
  • the blast furnace slag in the molten state (hereinafter referred to as 'melting blast furnace slag').
  • Molten blast furnace slag has a temperature of 1300 ⁇ 1600 °C.
  • the thermal energy of the molten blast furnace slag can reduce the use of electrical energy used in the electric furnace when manufacturing alumina cement can reduce the manufacturing cost.
  • the molten blast furnace slag may be a semi-melt or solid state as the cooling proceeds over time while passing through the transfer process or contained in the slag port to be supplied to the electric furnace, the molten blast furnace of the present invention Slag includes even this case.
  • the molten blast furnace slag is cooled to some extent it is preferable to have a temperature of more than 1000 °C.
  • FIG. 1 It is a schematic diagram for demonstrating an example of the alumina cement manufacturing method.
  • the molten blast furnace slag is discharged from the slag port, and the molten blast furnace slag is supplied to the electric furnace 20 located below the molten blast furnace slag tap water 10.
  • the electric furnace 20 is preferably provided with an electrode rod 30, it is preferable to energize the electrode rod 30 to maintain the temperature of the molten blast furnace slag. Thereafter, ladle slag, limestone and bauxite are introduced into the furnace in which the molten blast furnace slag is supplied.
  • the molten blast furnace slag provided in the electric furnace is 2 to 50% by weight, ladle slag 1 to 5% by weight, limestone is less than 27% by weight, bauxite is added to have a range of 45 to 80% by weight. desirable.
  • the injected ladle slag, limestone and bauxite are melted.
  • melting energy 1400 to 1800 MJ / ton is required, and for this, a temperature of 1400 to 1600 ° C. is required.
  • the present invention uses a blast furnace slag having a temperature of 1300 ⁇ 1600 °C, it is possible to obtain the effect of replenishing the required heat energy.
  • the ladle slag is also discharged in the molten state at the site. However, while the transfer process from the ladle to the electric furnace to supply to the electric furnace, the cooling proceeds to a semi-melt state or a solid state.
  • the cooling proceeds as described above, it usually has a temperature of 800 ⁇ 1000 °C, by using the high temperature ladle slag can secure the effect of replenishing the energy required for the melting of the raw material.
  • the ladle slag, limestone and bauxite may be naturally melted by the thermal energy possessed by the molten blast furnace slag, but the three electrode rods 30 provided in the electric furnace 20 for faster melting of raw materials It is preferable to melt the said raw material by energizing ().
  • the raw material melted as mentioned above is stirred in order to have a uniform component composition.
  • the two electrodes are energized at least two times during the stirring, and at this time, one of the two electrodes that are energized and an electrode that is not energized are used to allow the raw material to be stirred.
  • the electrode A 30A and electrode B 30B are energized and the electrode C 30C is not energized.
  • alternating current is generated in the C electrode rod 30C, and thus the raw material may be stirred.
  • the B electrode 30B and the C electrode 30C are energized, and the A electrode 30A is not energized so that an alternating current occurs at the A electrode 30A side, which is repeated sequentially.
  • the alternating current occurs in the entire furnace 20, the raw materials may be more uniformly mixed.
  • stirred raw material may be discharged from the electric furnace 20 and cooled to prepare alumina cement.
  • the alumina cement manufacturing method of the present invention provided as described above can reduce the amount of electrical energy required for the use of the electric furnace by 30 ⁇ 60% by using the heat energy due to the high temperature of the molten blast furnace slag and ladle slag, manufacturing The cost can be significantly lowered.
  • the alumina cement manufacturing method of the present invention may be provided with two or more electric furnaces. More specifically, the molten blast furnace slag can be continuously supplied through the tap water, but the production of alumina cement is made in a batch type. Therefore, two or more electric furnaces are provided so that supply of the said molten blast furnace slag can be performed continuously without stopping.
  • one of the two furnaces hereinafter referred to as 'first furnace'
  • the secondary raw materials such as ladle slag, limestone and bauxite are supplied inside the furnace. After feeding, the raw material is melted, agitated and discharged, and then cooled to prepare alumina cement.
  • molten blast furnace slag is converted into another electric furnace (hereinafter, 'second electric).
  • the supply of molten blast furnace slag can be made continuously by supplying to the furnace, and when this is repeated, continuous production of alumina cement can be performed to further improve productivity.
  • a variable cover 40 capable of preventing the supply of the molten blast furnace slag to the runway 10. Is preferably provided.
  • the cover supplies the blast furnace molten slag to the first electric furnace
  • the molten blast furnace slag is blocked so that the molten blast furnace slag is not supplied to the second electric furnace to prevent the transfer of the molten blast furnace slag, and the blast furnace molten slag is supplied to the second electric furnace.
  • the molten blast furnace slag may be alternately supplied by interrupting the flow of water on the first electric furnace side.
  • the molten blast furnace slag was used containing SiO 2 : 34% by weight, Al 2 O 3 : 18% by weight, Fe 2 O 3 : 1% by weight, CaO: 43% by weight, MgO: 3% by weight ,
  • the ladle slag was used containing 7 wt% SiO 2 , 36 wt% Al 2 O 3 : 2 wt% Fe 2 O 3 , 42 wt% CaO, 5 wt% MgO.
  • each component described in Table 2 above is the optimum compounding ratio for the production of alumina cement.
  • Table 2 the present inventors were able to manufacture alumina cements from 1 to 5 types while using as little as possible limestone and bauxite by controlling the blast furnace slag and ladle slag to an appropriate content. That is, the alumina cement provided by the present invention, unlike conventional alumina cement, uses molten blast furnace slag and high temperature ladle slag as a substitute for alumina cement raw material, thereby reducing the use of expensive raw materials, and using electric energy using sensible heat of the material. By reducing the use, the manufacturing cost can be reduced.
  • the alumina cement provided by the present invention has a condensation time of 300 to 600 minutes, similar to that of Portland cement (termination time: 300 to 420 minutes), but the compressive strength of portland cement. Considering that is typically 15 MPa after 1 day, 22.5 MPa after 3 days, 42.5 MPa after 28 days, the alumina cement of the present invention has a similar level of strength after 28 days of Portland cement after 1 day. It can be seen that it has strength.
  • each component described in Table 2 above is the optimum compounding ratio for the production of alumina cement.
  • Table 2 the present inventors were able to manufacture alumina cements from 1 to 5 types while using as little as possible limestone and bauxite by controlling the blast furnace slag and ladle slag to an appropriate content. That is, the alumina cement provided by the present invention, unlike conventional alumina cement, uses molten blast furnace slag and high temperature ladle slag as a substitute for alumina cement raw material, thereby reducing the use of expensive raw materials, and using electric energy using sensible heat of the material. By reducing the use, the manufacturing cost can be reduced.
  • the alumina cement provided by the present invention has a condensation time of 300 to 600 minutes, similar to that of Portland cement (termination time: 300 to 420 minutes), but the compressive strength of portland cement. Considering that is typically 15 MPa after 1 day, 22.5 MPa after 3 days, 42.5 MPa after 28 days, the alumina cement of the present invention has a similar level of strength after 28 days of Portland cement after 1 day. It can be seen that it has strength.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Environmental & Geological Engineering (AREA)
  • Civil Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

La présente invention concerne un ciment alumineux utilisant du laitier en fusion de haut-fourneau et du laitier de poche haute température, ainsi que son procédé de fabrication Selon un mode de réalisation, la présente invention concerne un ciment alumineux contenant de 2 à 50 % en poids de laitier de haut-fourneau, de 1 à 5 % en poids de laitier de poche, au maximum 27 % en poids de calcaire et de 45 à 80 % en poids de bauxite, ainsi que son procédé de fabrication. Selon la présente invention, le laitier en fusion de haut-fourneau et le laitier de poche haute température sont utilisés comme alternative aux matières premières du ciment alumineux, ce qui limite l'utilisation de matières premières coûteuses et réduit les coûts de fabrication grâce à la diminution de la consommation d'énergie électrique suite à l'utilisation de la chaleur sensible de la matière.
PCT/KR2013/006680 2012-10-31 2013-07-25 Ciment alumineux utilisant du laitier en fusion de haut-fourneau et du laitier de poche haute température, et son procédé de fabrication Ceased WO2014069751A1 (fr)

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Application Number Priority Date Filing Date Title
KR10-2012-0122134 2012-10-31
KR1020120122134A KR101342137B1 (ko) 2012-10-31 2012-10-31 용융 고로 슬래그 및 고온 래들 슬래그를 이용한 알루미나 시멘트 및 그 제조방법

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WO2014069751A1 true WO2014069751A1 (fr) 2014-05-08

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KR101567851B1 (ko) * 2015-07-21 2015-11-10 고재형 Kr파우더가 혼입된 친환경 폴리머 모르터르 및 이를 이용한 콘크리트 단면보수 보강방법

Citations (7)

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Publication number Priority date Publication date Assignee Title
JP2000313907A (ja) * 1990-07-25 2000-11-14 Chubu Steel Plate Co Ltd 電気炉スラグを原料とするクリンカーの製造方法
JP2001048614A (ja) * 1999-08-04 2001-02-20 Tomohiro Akiyama セメント類またはセメント添加物製造方法
JP2003137618A (ja) * 2001-11-02 2003-05-14 Kawatetsu Mining Co Ltd 無機混和材を含有する高炉スラグ微粉末、高炉セメント、および、それらの製造方法
US6676747B2 (en) * 2000-01-28 2004-01-13 Holcim Ltd. Method for producing puzzolanic binders for the cement industry from steel slags using a reduction metal bath
KR100415659B1 (ko) * 1998-11-25 2004-03-19 주식회사 포스코 레이들 슬래그를 이용한 시멘트 조성물 및 그 제조방법
KR100559506B1 (ko) * 2003-11-28 2006-03-15 요업기술원 정련 슬래그를 사용한 알루미나 시멘트 클링커의 제조방법
JP2006282486A (ja) * 2005-04-05 2006-10-19 Denki Kagaku Kogyo Kk アルミナセメント、アルミナセメント組成物及び不定形耐火物

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* Cited by examiner, † Cited by third party
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KR101046970B1 (ko) * 2008-12-05 2011-07-06 주식회사 제트콘코리아 콘크리트 구조물의 표면보호재로서 레이들 슬래그 결정성장반응을 이용한 마감재 조성물

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000313907A (ja) * 1990-07-25 2000-11-14 Chubu Steel Plate Co Ltd 電気炉スラグを原料とするクリンカーの製造方法
KR100415659B1 (ko) * 1998-11-25 2004-03-19 주식회사 포스코 레이들 슬래그를 이용한 시멘트 조성물 및 그 제조방법
JP2001048614A (ja) * 1999-08-04 2001-02-20 Tomohiro Akiyama セメント類またはセメント添加物製造方法
US6676747B2 (en) * 2000-01-28 2004-01-13 Holcim Ltd. Method for producing puzzolanic binders for the cement industry from steel slags using a reduction metal bath
JP2003137618A (ja) * 2001-11-02 2003-05-14 Kawatetsu Mining Co Ltd 無機混和材を含有する高炉スラグ微粉末、高炉セメント、および、それらの製造方法
KR100559506B1 (ko) * 2003-11-28 2006-03-15 요업기술원 정련 슬래그를 사용한 알루미나 시멘트 클링커의 제조방법
JP2006282486A (ja) * 2005-04-05 2006-10-19 Denki Kagaku Kogyo Kk アルミナセメント、アルミナセメント組成物及び不定形耐火物

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