WO2015111394A1 - 溶融金属容器のライニング構造体の製造方法及び溶融金属容器のライニング構造体 - Google Patents

溶融金属容器のライニング構造体の製造方法及び溶融金属容器のライニング構造体 Download PDF

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Publication number
WO2015111394A1
WO2015111394A1 PCT/JP2015/000185 JP2015000185W WO2015111394A1 WO 2015111394 A1 WO2015111394 A1 WO 2015111394A1 JP 2015000185 W JP2015000185 W JP 2015000185W WO 2015111394 A1 WO2015111394 A1 WO 2015111394A1
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WIPO (PCT)
Prior art keywords
refractory
lining
molten metal
magnesia
mass
Prior art date
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PCT/JP2015/000185
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English (en)
French (fr)
Japanese (ja)
Inventor
井上　明彦
清田　禎公
Original Assignee
Ｊｆｅスチール株式会社
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Application filed by Ｊｆｅスチール株式会社 filed Critical Ｊｆｅスチール株式会社
Priority to KR1020167022832A priority Critical patent/KR101929640B1/ko
Priority to JP2015517516A priority patent/JP5907312B2/ja
Priority to CN201580004938.3A priority patent/CN105917186B/zh
Publication of WO2015111394A1 publication Critical patent/WO2015111394A1/ja

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/16—Making or repairing linings increasing the durability of linings or breaking away linings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/02—Linings
    • 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
    • C04B35/10—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 aluminium oxide
    • 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
    • C04B35/10—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 aluminium oxide
    • C04B35/101—Refractories from grain sized mixtures
    • 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
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B7/00—Blast furnaces
    • C21B7/04—Blast furnaces with special refractories
    • C21B7/06—Linings for furnaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/28—Manufacture of steel in the converter
    • C21C5/42—Constructional features of converters
    • C21C5/44—Refractory linings
    • C21C5/441—Equipment used for making or repairing linings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/0003—Linings or walls
    • F27D1/0006—Linings or walls formed from bricks or layers with a particular composition or specific characteristics
    • 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
    • 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
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • 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
    • 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
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C04B2235/321—Dolomites, i.e. mixed calcium magnesium carbonates
    • 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
    • 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
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase

Definitions

  • the present invention relates to a manufacturing method of a lining structure of a molten metal container and a lining structure of a molten metal container.
  • the lining structures of various molten metal containers are the outer shells of the molten metal container.
  • steel shell is provided, and is made up of a permanent refractory and a lining refractory in order toward the inside of the molten metal container.
  • the working surface of the innermost refractory (working face refractory) is in contact with the molten metal.
  • the characteristics of the lining refractory in the molten metal container are required to have corrosion resistance against slag, which is a molten metal and a coexisting molten oxide, and resistance to spalling due to temperature change.
  • lining refractories containing alumina and magnesia undergo spinelization by sintering after construction.
  • the volume of the refractory expands as the spinelization progresses, and the voids present in the refractory decrease. Accordingly, the refractory can be densified to reduce the porosity, and the slag can be prevented from entering the refractory, so that the wear rate of the refractory can be reduced.
  • Patent Document 1 alumina and magnesia that are not spineled are used as main materials as the refractory for the lining, and after the refractory for the lining is applied, firing is performed at a high temperature of 1300 ° C. or more for 4 hours or more. By doing so, it is disclosed to spinel the refractory for lining before using the molten metal container.
  • Patent Document 2 proposes that a small amount of silica (silica) that lowers the melting point is added to rapidly advance spinelization.
  • Patent Document 2 a small amount of silica that lowers the melting point is added and a liquid phase is partially generated, so that a rapid spinel formation is achieved with respect to normal solid phase diffusion.
  • the decrease in fire resistance due to the addition of silica impairs the advantage of spinelization that densifies the refractory and prevents the intrusion of slag.
  • fire resistance is inferior compared to.
  • the present invention has been made for such a problem, and does not require a strong burner facility as in the prior art, and a method for producing a molten metal container lining structure having sufficient fire resistance and melting
  • An object of the present invention is to provide a lining structure for a metal container.
  • Non-fired refractory containing 60% by mass or more of alumina and 4% by mass or more of magnesia as the lining refractory and having a linear change rate at room temperature of 0.8% or more before and after heat treatment at 1500 ° C. for 3 hours.
  • the manufacturing method of the lining structure of a molten metal container which preheats the working surface of the said lining refractory before using the said molten metal container.
  • the lining refractory before construction contains 50% by mass or more of the magnesia as periclase or calcined dolomite, In the preheating before use of the molten metal container, the molten metal container according to [1], wherein in the lining refractory before construction, a part of magnesia that is periclase or calcined dolomite is preheated until it is spineled with alumina.
  • Method for manufacturing the lining structure of the present invention [3] A molten metal container lining structure manufactured by the method for manufacturing a molten metal container lining structure according to [1] or [2].
  • the manufacturing method of the lining structure of the molten metal container which has sufficient fireproof performance, and the lining structure of a molten metal container which do not require the strong burner installation like the past can be provided. .
  • FIG. 1 is a view showing a lining structure of a molten metal container according to an embodiment of the present invention.
  • FIG. 2 is a diagram showing the relationship between the distance from the working surface of the lining refractory according to Invention Example 1 (with heat insulation) and Comparative Example 3 (without heat insulation) and the spinelization ratio of magnesia.
  • the present invention uses a material that can spinel alumina and magnesia as the lining refractory after the lining refractory construction, while providing a heat insulating layer between the iron skin and the permanent refractory. It was discovered that by installing it, the refractory cost could be greatly reduced without deteriorating the equipment cost and energy cost, and it was completed.
  • a heat insulating layer is provided on the iron skin side of the lining refractory.
  • the ratio of spinel formation during preheating after construction is increased, and spinelization is further advanced to a sufficiently deep portion, so that the expansion associated with the progress of spinelization after the start of actual use, that is, after the operation of the lining refractory starts. It is possible to reduce cracks and suppress cracks. Thereby, the refractory cost can be greatly reduced without deteriorating the equipment cost and the energy cost.
  • the back surface of the lining refractory refers to a surface opposite to the working surface, that is, the surface in contact with the molten metal.
  • FIG. 1 is a view showing an example of a lining structure of a molten metal container according to an embodiment of the present invention.
  • An iron skin 1 is provided on the outermost side of the molten metal container.
  • the lining structure is in contact with molten metal (not shown) on the inner side, that is, on the right side of the drawing.
  • the lining structure includes a heat insulating material 2, a permanent refractory material 3, and a lining refractory material 4 in order from the iron skin 1 to the inside, that is, in the direction in which molten metal enters (lining direction).
  • the heat insulating material 2 has a heat transfer coefficient of 100 W / m 2 K or less.
  • the heat transfer coefficient of the permanent refractory 3 is about 100 W / m 2 K.
  • the heat transfer coefficient is a value obtained by dividing the thermal conductivity of each refractory layer such as the lining refractory 4, the permanent refractory 3, and the heat insulating material 2 by the thickness of each layer.
  • the heat insulating material 2 As a heat insulating material having a heat transfer coefficient of 100 W / m 2 K or less, which is lower than that of the permanent refractory 3, the temperature gradient inside the lining refractory 4 is gradually reduced, In addition, the temperature up to the back surface can be increased, and spinelization of the lining refractory 4 can be sufficiently advanced by preheating before use. Since the heat insulating material 2 is generally porous and has low fire resistance, the heat insulating material 2 is provided between the iron shell 1 and the permanent refractory 3 in order to keep the temperature of the heat insulating material 2 low.
  • the thermal conductivity of an inexpensive heat insulating material is about 0.3 W / mK. If such a heat insulating material is applied as the heat insulating material 2 and the construction thickness is 3 mm, the heat transfer coefficient is 100 W / m 2 K. For example, the construction thickness is doubled to 6 mm, the heat transfer coefficient is lowered to 50 W / m 2 K, or the heat conductivity is about 0.03 W / mK, although it is somewhat expensive, If the heat transfer coefficient can be lowered to 10 W / m 2 K, the effect of the present invention is further increased.
  • the permanent refractory 3 is usually made of brick such as alumina and has a joint filled with mortar.
  • the heat transfer coefficient of the permanent refractory 3 is about 100 W / m 2 K. Although illustrated as one layer in FIG. 1, two layers of the permanent refractory 3 may be provided.
  • the lining refractory 4 is an unfired refractory and / or an amorphous refractory in which alumina and magnesia are spineled by sintering after application of the refractory, including alumina and magnesia.
  • the “non-fired refractory” refers to a refractory that is not fired in advance after molding and before construction
  • the “indefinite refractory” refers to a refractory that is not previously molded before construction.
  • the lining refractory 4 is preferably composed of one or both of an unfired refractory and an amorphous refractory containing 60% by mass or more of alumina and 4% by mass or more of magnesia. More preferably, it is preferable that the lining refractory 4 contains 80% by mass or more of alumina and 5% by mass or more of magnesia except when graphite or the like is blended for a special application.
  • the lining refractory 4 before spinelizing alumina and magnesia 50 mass% or more of magnesia is included in the refractory as periclase or baked dolomite.
  • the ratio which turns into a spinel after construction can be made high, the effect which densifies the lining refractory 4 and improves corrosion resistance is acquired.
  • it is more preferable that 90% by mass or more of magnesia is supplied as periclase.
  • the unfired refractory and / or the amorphous refractory constituting the lining refractory 4 has a linear change rate at room temperature before and after heat treatment at 1500 ° C.
  • line change after heat treatment at 1500 ° C. The rate is also adjusted to 0.8% or more.
  • the linear change rate after heat treatment at 1500 ° C. to 0.8% or more, in the case of the lining structure including the heat insulating material 2 described above, after use as a molten metal container during preheating after refractory construction ( After operation), the effect of improving the corrosion resistance by densifying the lining refractory 4 by spineling of alumina and magnesia is obtained.
  • the heat treatment temperature is set to 1500 ° C.
  • the heat treatment time is set to 3 hours, considering the temperature history on the working surface side of the lining refractory 4 after use (after operation) as a molten metal container, and a lining by spinel formation. This is because the refractory 4 is used as an index of densification.
  • the linear change rate at room temperature after heat treatment at 1500 ° C. is less than 0.8%, the effect of improving the corrosion resistance by densifying the lining refractory 4 even when the lining structure including the heat insulating material 2 is used. Is not enough.
  • the lining structure that does not include the layer of the heat insulating material 2 if the linear change rate at room temperature after heat treatment at 1500 ° C.
  • the linear change rate at room temperature after heat treatment at 1500 ° C. is 1.5% or more in order to improve the corrosion resistance by densifying the lining refractory 4.
  • the linear change rate after heat treatment at 1500 ° C. is a method in which the positive value corresponds to expansion and the negative value corresponds to contraction, respectively, and the content of magnesia in the refractory to be contained in the refractory as periclase or baked dolomite is increased. And can be adjusted to decrease by a method such as increasing the content of titania, iron oxide, and silica contained in the refractory as impurities.
  • a material containing 60% by mass of alumina and 4% by mass or more of magnesia can sufficiently exhibit the effect of improving corrosion resistance by spinelization. Can do.
  • the effect of promoting the spinelization of the lining refractory 4 is a molten metal. Appears in the drying / preheating process of the lining refractory 4 before use of the container.
  • the temperature of the working surface of the lining refractory 4 can be raised to 800 ° C. by providing the heat insulating material 2 having a heat transfer coefficient of 100 W / m 2 K or less on the back side of the lining refractory 4. In this case, spinelization of the lining refractory 4 in the vicinity of the working surface can be sufficiently advanced.
  • the surface (working surface) temperature of the lining refractory at the end of the drying / preheating process is more preferably 900 to 1200 ° C.
  • the inner refractory 4 is 91 mass% alumina-6 mass% magnesia, and 5/6 of magnesia (mass basis) is preliminarily blended as alumina-magnesia spinel at 1500 ° C.
  • a cast amorphous refractory material having a linear change rate of 0.1% at room temperature after the heat treatment was used.
  • the heat insulating sheet 2 was not constructed.
  • the heat transfer coefficient of the permanent refractory 3 is 100 W / m 2 K. The lifetime was 225 heat.
  • the infiltration depth of calcium oxide or silica, which is a slag component, into the refractory is as deep as 40 mm compared to the usual 30 mm, and cracks at the boundary was also recognized.
  • Comparative Example 4 As the lining refractory 4, a non-cast refractory made of a material in which 94% by mass of alumina-3% by mass magnesia and 95% by mass or more of magnesia was blended as periclase was used. An insulation sheet was constructed. As a result, the life of the lining refractory 4 was longer than that of the conventional example but shorter than that of Comparative Example 3. This is because even when magnesia with a high periclase ratio is used, if the total amount of magnesia is less than 4% by mass, the linear change rate at room temperature after heat treatment at 1500 ° C. is as low as 0.7%, and the effect of densifying the refractory is sufficient.
  • the life extension by changing the material of the lining refractory 4 is 11%, which is the extension of the life of the comparative example 3, and in addition to this, the life extension by providing a layer of the heat insulating material 2 is an example of the present invention. This is considered to be 22%, which is the difference in the extension of the lifetime between 1 and Comparative Example 3.
  • FIG. 2 is a diagram showing the relationship between the distance from the working surface of the lining refractory and the magnesia spinelization ratio in Invention Example 1 (with heat insulating material) and Comparative Example 3 (without heat insulating material).
  • the thickness of the lining refractory 4 is 130 mm.
  • Example 1 of the present invention that has the heat insulating material 2
  • the spinelization ratio is 24 to 30 points higher in each part, particularly in the central portion having a depth of 56 to 75 mm.
  • the ratio was 35% with respect to 11%, and the ratio of spinelization was 3.2 times that of Comparative Example 3.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Structural Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)
  • Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Ceramic Products (AREA)
PCT/JP2015/000185 2014-01-23 2015-01-16 溶融金属容器のライニング構造体の製造方法及び溶融金属容器のライニング構造体 WO2015111394A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020167022832A KR101929640B1 (ko) 2014-01-23 2015-01-16 용융 금속 용기의 라이닝 구조체의 제조 방법 및 용융 금속 용기의 라이닝 구조체
JP2015517516A JP5907312B2 (ja) 2014-01-23 2015-01-16 溶融金属容器のライニング構造体の製造方法
CN201580004938.3A CN105917186B (zh) 2014-01-23 2015-01-16 熔融金属容器的衬里结构体的制造方法及熔融金属容器的衬里结构体

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JP2014010237 2014-01-23
JP2014-010237 2014-01-23

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WO2015111394A1 true WO2015111394A1 (ja) 2015-07-30

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KR (1) KR101929640B1 (zh)
CN (1) CN105917186B (zh)
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
JP2017180855A (ja) * 2016-03-28 2017-10-05 Ｊｆｅスチール株式会社 耐火物構造
JP2020006395A (ja) * 2018-07-06 2020-01-16 新東工業株式会社 鋳鋼鋳物製造システム

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Publication number Priority date Publication date Assignee Title
EA202090334A1 (ru) 2017-08-29 2020-10-07 ВЕЗУВИУС ЮЭсЭй КОРПОРЕЙШН Конструкция огнеупорной футеровки

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