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WO2019131082A1 - 熱間補修用吹付材 - Google Patents

熱間補修用吹付材 Download PDF

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Publication number
WO2019131082A1
WO2019131082A1 PCT/JP2018/045271 JP2018045271W WO2019131082A1 WO 2019131082 A1 WO2019131082 A1 WO 2019131082A1 JP 2018045271 W JP2018045271 W JP 2018045271W WO 2019131082 A1 WO2019131082 A1 WO 2019131082A1
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WO
WIPO (PCT)
Prior art keywords
mass
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content
magnesia
spray
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/045271
Other languages
English (en)
French (fr)
Inventor
本田　和寛
統一 白曼
哲 赤井
翼 中道
洋輔 大野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Krosaki Harima Corp
Original Assignee
Krosaki Harima Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Krosaki Harima Corp filed Critical Krosaki Harima Corp
Priority to EP18895424.2A priority Critical patent/EP3733631B1/en
Priority to CN201880052866.3A priority patent/CN111032596B/zh
Priority to PL18895424.2T priority patent/PL3733631T3/pl
Priority to ES18895424T priority patent/ES2988274T3/es
Priority to AU2018394519A priority patent/AU2018394519B2/en
Publication of WO2019131082A1 publication Critical patent/WO2019131082A1/ja
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
    • 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
    • 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
    • C04B35/63—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 using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63472—Condensation polymers of aldehydes or ketones
    • C04B35/63476—Phenol-formaldehyde condensation polymers
    • 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
    • C04B35/63—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 using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63496—Bituminous materials, e.g. tar, pitch
    • 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
    • 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
    • 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; Breaking away linings
    • F27D1/1636—Repairing linings by projecting or spraying refractory materials on the lining
    • 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
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • 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
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5463—Particle size distributions
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5463—Particle size distributions
    • C04B2235/5472—Bimodal, multi-modal or multi-fraction
    • 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
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • 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
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
    • C04B2235/9676—Resistance against chemicals, e.g. against molten glass or molten salts against molten metals such as steel or aluminium

Definitions

  • the present invention relates to, for example, a spray material for hot repair which is used for hot repair of the lining of a converter, degassing furnace, ladle and other kilns and sprayed onto a surface to be repaired with construction water.
  • hot repair refers to repair when the temperature of the surface to be repaired is approximately 600 ° C. or higher.
  • the converter it is practiced to repair the melting point of the lining hot.
  • a method of hot repair a method is known in which a spray material containing a refractory material and a binder is sprayed to the erosion point of the lining along with the construction water.
  • phosphate or silicate forms a low melting point compound together with slag. It has the disadvantage of poor durability.
  • Patent Document 1 in order to prevent the softening of the carbonaceous resin from being delayed, a part of the carbonaceous resin is blended with the powder to be granulated in a state where the granulated product is formed, but the granulated material is As a result, it is difficult to transfer heat to the carbonaceous resin. For this reason, the softening delay of the carbonaceous resin can not be avoided, and the spraying material rebounds when it reaches the surface to be repaired, and there is a problem that the adhesion to the surface to be repaired is inferior.
  • the problem to be solved by the present invention is to improve the adhesion to the surface to be repaired in the hot repair spray material.
  • the present inventors considered that it is effective to use a phenol resin as the carbonaceous resin in order to improve the adhesion to the surface to be repaired (hereinafter simply referred to as "adhesion"). That is, it is because it is easy for the phenol resin to coagulate at the moment it is sprayed on the surface to be repaired and to exhibit appropriate viscosity (adhesiveness). Moreover, the present inventors selected the magnesia-based material as the refractory material from the viewpoint of improving the durability such as the slag permeability.
  • the present inventors came to think of the present invention as a result of repeating studies focusing on the blending ratio of the magnesia raw material and the phenol resin, particularly the blending ratio of the ultrafine powder region. .
  • the following hot repair spray material is provided. 65 mass% or more and 95 mass% or less of a magnesia-based material, and 0.5 mass% or more and 10 mass% or less of a phenol resin, And, the content of the magnesia-based material having a particle size of less than 20 ⁇ m is 5% by mass to 30% by mass, and the content of a phenol resin having a particle size of less than 20 ⁇ m is 0.3% by mass to 9% by mass.
  • the hot repair spray material wherein “the content of the magnesia-based material having a particle diameter of less than 20 ⁇ m / the content of the phenol resin having a particle diameter of less than 20 ⁇ m” is 0.6 to 30.
  • the blending ratio of the magnesian raw material and the phenolic resin in a very active ultrafine powder area having a particle size of less than 20 ⁇ m is within a specific range, and the magnesian raw material and the phenolic resin are well balanced in the ultrafine powder area. Because of the presence, a matrix having an appropriate viscosity (adhesiveness) is formed at the moment of spraying, and furthermore, uniform carbon bonds are formed in this matrix. This improves adhesion.
  • the spray material for hot repair according to the present invention contains 65 mass% or more and 95 mass% or less of the magnesia-based material, and 0.5 mass% or more and 10 mass% or less of the phenol resin.
  • the content of the magnesia-based material is less than 65% by mass, the durability such as corrosion resistance (slag resistance) is reduced.
  • the content of the magnesia-based material exceeds 95% by mass, the content of the phenolic resin is relatively reduced, and the adhesion is reduced.
  • the content of the phenol resin is less than 0.5% by mass, the effect of forming carbon bonds is weakened, and the adhesion is reduced.
  • the content of the phenolic resin exceeds 10% by mass, the structure of the spray construction body becomes porous because the volatilization from the phenol resin is large, and the strength of the spray construction body decreases.
  • the present invention limits the blending ratio of the magnesian raw material and the phenolic resin in the ultrafine powder region having a particle size of less than 20 ⁇ m. That is, the content of the magnesia-based material having a particle size of less than 20 ⁇ m is 5% by mass to 30% by mass, and the content of the phenol resin having a particle size of less than 20 ⁇ m is 0.3% by mass to 9% by mass.
  • the ratio “content of magnesian raw material with particle size less than 20 ⁇ m / phenol resin content with particle size less than 20 ⁇ m” (hereinafter, this content ratio is simply referred to as “content ratio”) is 0.6 or more 30 It is below.
  • the reason for limiting the blending ratio such as the content ratio is as follows.
  • the aggregation effect (adhesion retention function by aggregation) of the ultrafine powder of the magnesia-based material is weakened, and the adhesion is reduced. If the content of the magnesia-based material having a particle size of less than 20 ⁇ m exceeds 30% by mass, the aggregation effect becomes excessive and the viscosity becomes high, so that the dischargeability at the time of spray construction becomes worse, and as a result, the adhesion also decreases.
  • the reaction for forming a carbon bond is delayed and the adhesion is reduced. If the content of the phenolic resin having a particle size of less than 20 ⁇ m exceeds 9% by mass, the powder will float due to dusting at the time of spray construction, resulting in a decrease in adhesion. Furthermore, there is a problem that the installation location can not be seen because the suspended ultrafine phenolic resin burns.
  • the content ratio is less than 0.6 (when there is a large amount of ultrafine powder phenolic resin), the rate of volatilization of the phenolic resin becomes fast and the spray construction body shrinks at a stretch, the spray construction body floats at the adhesion interface, descend. And, with the decrease in the adhesive force, peeling occurs due to the weight of the sprayed construction body and the sprayed pressure.
  • the content ratio exceeds 30 (when the amount of the ultrafine powder phenolic resin is small), the strength after adhesion can not be maintained, and the spray construction body falls off.
  • the preferable range of this content ratio is 0.6 or more and 20 or less.
  • magnesian raw material and the phenol resin used in the present invention those generally used (commercially available) as a raw material of a hot repair spraying material can be used. And, the particle size constitution of these magnesian raw materials and phenol resin may be adjusted so that the content and the content ratio of those having a particle diameter of less than 20 ⁇ m fall within the above-described predetermined range.
  • a part of magnesian raw material can be an aggregate, so for example, in the particle size range of less than 4 mm in particle diameter, the content and content ratio of particles less than 20 ⁇ m in particle diameter The particle size may be adjusted to be within the predetermined range.
  • magnesia-based material refers to a material having an MgO content of 60% by mass or more, and includes not only natural magnesia materials but also scraps of magnesia bricks and magnesia-carbon bricks.
  • particle size in the present invention is a sieve, and for example, a particle size of less than 20 ⁇ m means one that has passed a sieve of 20 ⁇ m.
  • the spray material for hot repair of the present invention can contain 0.5 mass% or more and 10 mass% or less of the pitch in addition to the magnesia-based material and the phenol resin. By containing 0.5% by mass or more and 10% by mass or less of the pitch, the strength of the sprayed construction can be improved and the durability can be improved.
  • the spray material for hot repair is a spray for hot repair such as dolomite raw material and other refractory raw materials such as carbon raw material, metal powder, organic fiber, etc. What is generally used as a raw material of material can be contained suitably.
  • the hot-repairing spray material of the present invention is sprayed onto the surface to be repaired together with the construction water similarly to the conventional hot-repairing spray material, but the spraying conditions such as the addition amount of the construction water and the spraying method are the same as conventional. Good.
  • Table 1 shows the blending of raw materials and evaluation results of the examples and comparative examples of the present invention. Evaluation items and evaluation methods in the examples and comparative examples are as follows.
  • “other raw materials” are dolomite raw materials, carbon raw materials, and metal powder.
  • ⁇ Adhesiveness> The spray material of each example was sprayed onto the vertical surface (surface to be repaired) of magnesia-carbon brick heated to about 1000 ° C. using a conventional dry sprayer to form a spray applied body.
  • the amount of the construction water added was 20 to 40% by mass with respect to 100% by mass of the spray material.
  • the adhesion is evaluated by the adhesion ratio of the spray material to the surface to be repaired, and the ratio of the adhesion amount to the surface to be repaired to the usage amount of the spray material is 80% by mass or more, ⁇ (good), 60 mass% or more
  • the case of less than 80% by mass was regarded as ⁇ (acceptable), and the case of less than 60% by mass was regarded as x (impossible).
  • Comparative Example 1 is an example in which the content of the magnesia raw material is small. Sufficient corrosion resistance was not obtained because the amount of magnesia-based material contributing to the improvement of corrosion resistance (slag penetration resistance) is small.
  • Comparative Example 2 is an example in which the content of the magnesia raw material is large. The content of the phenolic resin relatively decreased, and the adhesion decreased to such an extent that a sufficient sprayed construction could not be obtained. Therefore, the sample for evaluating corrosion resistance and spray construction body intensity was not able to be taken.
  • Comparative Example 3 is an example in which the content of the magnesia starting material having a particle size of less than 20 ⁇ m is small. The aggregation effect of the magnesia-based material having a particle size of less than 20 ⁇ m was weakened, and the adhesion was reduced. Comparative Example 4 is an example in which the content of the magnesia raw material having a particle size of less than 20 ⁇ m is large. The cohesion effect becomes excessive and the dischargeability at the time of the spray construction is deteriorated, and as a result, the adhesion is lowered to such an extent that a sufficient spray construction body can not be obtained. Therefore, the sample for evaluating corrosion resistance and spray construction body intensity was not able to be taken.
  • Comparative Example 5 is an example in which the content of the phenol resin is small and the content ratio is high (the content of the phenol resin having a particle diameter of less than 20 ⁇ m is small). Since the amount of the phenol resin contributing to the improvement of the adhesion is small, the adhesion is lowered to such an extent that a sufficient spray construction body can not be obtained. Therefore, the sample for evaluating corrosion resistance and spray construction body intensity was not able to be taken.
  • Comparative Example 6 is an example in which the content of the phenolic resin is large and the content ratio is low (the content of the phenolic resin having a particle diameter of less than 20 ⁇ m is large). The rate of volatilization of the phenolic resin was increased, and the phenolic resin having a particle size of less than 20 ⁇ m floated due to dust generation during the spray application, resulting in a decrease in adhesion.

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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)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Products (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)

Abstract

本発明は、熱間補修用吹付材において、吹き付けられた瞬間の被補修面への付着性を向上させることを目的とする。本発明の熱間補修用吹付材は、マグネシア質原料を６５質量％以上９５質量％以下、フェノール樹脂を０．５質量％以上１０質量％以下含有し、かつ、粒径２０μｍ未満のマグネシア質原料の含有量が５質量％以上３０質量％以下、粒径２０μｍ未満のフェノール樹脂の含有量が０．３質量％以上９質量％以下であり、「前記粒径２０μｍ未満のマグネシア質原料の含有量／前記粒径２０μｍ未満のフェノール樹脂の含有量」が０．６以上３０以下である。

Description

熱間補修用吹付材
　本発明は、例えば、転炉、脱ガス炉、取鍋、その他の窯炉の内張りの熱間補修に用いられ、施工水と共に被補修面に吹き付けられる熱間補修用吹付材に関する。
　なお、本発明において「熱間補修」とは、被補修面の温度が概ね６００℃以上の状態における補修のことをいう。
　例えば、転炉において、内張りの溶損箇所を熱間で補修することが行われている。熱間補修の方法として、耐火原料と結合剤とを含む吹付材を施工水と共に内張りの溶損箇所に吹き付ける方法が知られている。
　従来、この方法に使用される吹付材には、結合剤にリン酸塩やケイ酸塩を用いたものが多用されてきたが、リン酸塩やケイ酸塩は、スラグと共に低融点化合物を形成するため耐用性が悪いという欠点をもつ。
　そこで、近年では、吹付施工体に耐スラグ浸透性及び強度を付与する目的でリン酸塩やケイ酸塩に代えて、熱間でカーボンボンドを形成する物質、具体的にはフェノール樹脂等の炭素質樹脂が用いられている（例えば、特許文献１参照）。
特開２０１０－２３５３４０号公報
　特許文献１では、炭素質樹脂の軟化が遅延することを抑制するために、炭素質樹脂の一部を被造粒粉体と共に造粒物を形成した状態で配合しているが、造粒物を形成する以上、炭素質樹脂に熱が伝わりにくい。このため、炭素質樹脂の軟化遅延は避けられず、吹付材が被補修面に到達した際にリバウンドしてしまい、被補修面への付着性に劣るという問題があった。
　本発明が解決しようとする課題は、熱間補修用吹付材において、被補修面への付着性を向上させることにある。
　本発明者らは、被補修面への付着性（以下、単に「付着性」という。）を向上させるには、炭素質樹脂としてフェノール樹脂を用いることが有効と考えた。すなわち、フェノール樹脂は被補修面に吹き付けられた瞬間に凝集して適正な粘性（接着性）を発揮しやすいからである。また、本発明者らは耐スラグ浸透性等の耐用性を向上させる点から耐火原料としてマグネシア質原料を選択した。さらに、本発明者らは前記課題を解決するために、マグネシア質原料とフェノール樹脂の配合割合、特に超微粉域の配合割合に着目して検討を重ねた結果、本発明を想到するに至った。
　すなわち、本発明の一観点によれば次の熱間補修用吹付材が提供される。
　マグネシア質原料を６５質量％以上９５質量％以下、フェノール樹脂を０．５質量％以上１０質量％以下含有し、
　かつ、粒径２０μｍ未満のマグネシア質原料の含有量が５質量％以上３０質量％以下、粒径２０μｍ未満のフェノール樹脂の含有量が０．３質量％以上９質量％以下であり、
　「前記粒径２０μｍ未満のマグネシア質原料の含有量／前記粒径２０μｍ未満のフェノール樹脂の含有量」が０．６以上３０以下である熱間補修用吹付材。
　本発明によれば、粒径２０μｍ未満という非常に活性の高い超微粉域におけるマグネシア質原料とフェノール樹脂の配合割合が特定の範囲内にあり、超微粉域においてマグネシア質原料とフェノール樹脂がバランス良く存在することから、吹き付けられた瞬間に適正な粘性（接着性）を有するマトリクスが形成され、さらにこのマトリクス内に均一なカーボンボンドが形成される。これにより付着性が向上する。
　本発明の熱間補修用吹付材は、マグネシア質原料を６５質量％以上９５質量％以下、フェノール樹脂を０．５質量％以上１０質量％以下含有する。
　マグネシア質原料の含有量が６５質量％未満であると耐食性（耐スラグ浸透性）等の耐用性が低下する。マグネシア質原料の含有量が９５質量％を超えると、相対的にフェノール樹脂の含有量が少なくなり付着性が低下する。
　また、フェノール樹脂の含有量が０．５質量％未満であるとカーボンボンドを形成する効果が弱くなり付着性が低下する。フェノール樹脂の含有量が１０質量％を超えると、フェノール樹脂からの揮発が多いため吹付施工体の組織がポーラスになり、吹付施工体強度が低下する。
　本発明は前述のとおり、粒径２０μｍ未満という超微粉域におけるマグネシア質原料とフェノール樹脂の配合割合を限定する。すなわち、粒径２０μｍ未満のマグネシア質原料の含有量は５質量％以上３０質量％以下、粒径２０μｍ未満のフェノール樹脂の含有量は０．３質量％以上９質量％以下であり、その含有量比「前記粒径２０μｍ未満のマグネシア質原料の含有量／前記粒径２０μｍ未満のフェノール樹脂の含有量」（以下、この含有量比を単に「含有量比」という。）は０．６以上３０以下である。このように含有量比等の配合割合を限定する理由は以下のとおりである。
　粒径２０μｍ未満のマグネシア質原料の含有量が５質量％未満であると、この超微粉のマグネシア質原料が有する凝集効果（凝集による付着性保持機能）が弱くなり、付着性が低下する。粒径２０μｍ未満のマグネシア質原料の含有量が３０質量％を超えると、凝集効果が過大になってしまい粘性が高くなるため吹付施工時の吐出性が悪くなり、その結果付着性も低下する。
　粒径２０μｍ未満のフェノール樹脂の含有量が０．３質量％未満であると、カーボンボンドを形成する反応が遅くなってしまい付着性が低下する。粒径２０μｍ未満のフェノール樹脂の含有量が９質量％を超えると、吹付施工時に発塵により浮遊してしまい付着性が低下する。さらに、浮遊した超微粉のフェノール樹脂が燃焼するため、施工箇所が見えなくなる問題もある。
　含有量比が０．６未満の場合（超微粉のフェノール樹脂が多い場合）、フェノール樹脂の揮発速度が速くなり一気に吹付施工体が収縮し、接着界面で吹付施工体が浮いてしまい付着性が低下する。そして付着力低下に伴い、吹付施工体自重や吹付圧によって剥落が生じる。一方、含有量比が３０を超える場合（超微粉のフェノール樹脂が少ない場合）、付着した後の強度を保つことができずに吹付施工体が脱落する。この含有量比の好ましい範囲は０．６以上２０以下である。
　本発明に使用するマグネシア質原料及びフェノール樹脂としては、熱間補修用吹付材の原料として一般的に使用（市販）されているものを使用することができる。そして、これらマグネシア質原料及びフェノール樹脂の粒度構成は、粒径２０μｍ未満のものの含有量や含有量比が前述した所定の範囲内になるように調整すればよい。ここで、本発明の熱間補修用吹付材においてマグネシア質原料の一部は骨材となり得るので、例えば粒径４ｍｍ未満の粒度域で、粒径２０μｍ未満のものの含有量や含有量比が前述した所定の範囲内になるように粒度調整すればよい。
　なお、本発明でいう「マグネシア質原料」とはＭｇＯ含有量が６０質量％以上のものをいい、天然のマグネシア原料のほか、マグネシアれんがやマグネシア・カーボンれんがの屑も含むものである。
　また、本発明でいう「粒径」とは篩目のことであり、例えば粒径２０μｍ未満とは２０μｍの篩目を通過したものをいう。
　本発明の熱間補修用吹付材は、マグネシア質原料及びフェノール樹脂に加え、ピッチを０．５質量％以上１０質量％以下含有することができる。ピッチを０．５質量％以上１０質量％以下含有することで、吹付施工体強度が向上し耐用性を向上させることができる。
　なお、本発明の熱間補修用吹付材は、マグネシア質原料、フェノール樹脂及びピッチのほかにも、ドロマイト原料や炭素原料などの他の耐火原料、金属粉、有機繊維等、熱間補修用吹付材の原料として一般的に使用されているものを適宜含有することができる。
　本発明の熱間補修用吹付材は、従来の熱間補修用吹付材と同様に施工水と共に被補修面に吹き付けられるが、施工水の添加量などの吹付条件や吹付方法は従来と同様でよい。
　表１に本発明の実施例及び比較例の原料配合と評価結果を示している。実施例及び比較例における評価項目と評価方法は以下のとおりである。なお、表１中、「その他原料」とはドロマイト原料、炭素原料及び金属粉である。
＜付着性＞
　各例の吹付材を、慣用の乾式吹付機を用い、約１０００℃に熱したマグネシア・カーボンれんがの垂直面（被補修面）に吹き付け、吹付施工体を形成した。施工水の添加量は、吹付材１００質量％に対する外掛けで２０～４０質量％とした。
　付着性は、被補修面への吹付材の付着割合で評価し、吹付材の使用量に対する被補修面への付着量の割合が８０質量％以上の場合を〇（良）、６０質量％以上８０質量％未満の場合を△（可）、６０質量％未満の場合を×（不可）とした。
＜耐食性＞
　吹付施工体から切り出した所定寸法の試料を、回転侵食試験機を用い、Ｃ／Ｓ＝３．４の転炉スラグと鋼片とを侵食剤として、１６５０～１７００℃で５時間侵食させた。各例の最大溶損量を測定しかつその逆数を求め、実施例１のその逆数を１００とした相対値を求めた。この相対値が大きいほど耐食性に優れるということである。耐食性の評価では、この相対値が８０以上の場合を〇（良）、７０以上８０未満の場合を△（可）、７０未満を×（不可）とした。
＜吹付施工体強度＞
　吹付施工体から切り出した所定寸法の試料について、ＪＩＳＲ２５７５に従い常温での圧縮強度を測定し、実施例１の圧縮強度を１００とした相対値を求めた。この相対値が大きいほど吹付施工体強度が高いということである。吹付施工体強度の評価では、この相対値が８０以上の場合を〇（良）、７０以上８０未満の場合を△（可）、７０未満を×（不可）とした。
＜吐出性＞
　吹付時に乾式吹付機のノズル先端を目視観察し、脈動なく吐出している場合を〇（良）、脈動がある場合を×（不可）とした。
＜総合評価＞
　前記各評価項目の評価が全て○の場合を○（良）、△が１～３つであってその他が〇の場合を△（可）、いずれか１つが×の場合を×（不可）とした。
Figure JPOXMLDOC01-appb-T000001
　表１に示しているように本発明の範囲内にある実施例１～６は、付着性の評価が○（良）又は△（可）で良好であり、総合評価も良好であった。
　比較例１はマグネシア質原料の含有量が少ない例である。耐食性（耐スラグ浸透性）向上に寄与するマグネシア質原料が少ないため、十分な耐食性が得られなかった。
　比較例２はマグネシア質原料の含有量が多い例である。相対的にフェノール樹脂の含有量が少なくなり、十分な吹付施工体が得られないほどに付着性が低下した。そのため耐食性及び吹付施工体強度を評価するための試料が取れなかった。
　比較例３は粒径２０μｍ未満のマグネシア質原料の含有量が少ない例である。粒径２０μｍ未満のマグネシア質原料が有する凝集効果が弱くなり、付着性が低下した。
　比較例４は粒径２０μｍ未満のマグネシア質原料の含有量が多い例である。凝集効果が過大になってしまい、吹付施工時の吐出性が悪化し、その結果、十分な吹付施工体が得られないほどに付着性が低下した。そのため耐食性及び吹付施工体強度を評価するための試料が取れなかった。
　比較例５はフェノール樹脂の含有量が少なく、含有量比が高い（粒径２０μｍ未満のフェノール樹脂の含有量が少ない）例である。付着性向上に寄与するフェノール樹脂が少ないため、十分な吹付施工体が得られないほどに付着性が低下した。そのため耐食性及び吹付施工体強度を評価するための試料が取れなかった。
　比較例６はフェノール樹脂の含有量が多く、含有量比が低い（粒径２０μｍ未満のフェノール樹脂の含有量が多い）例である。フェノール樹脂の揮発速度が速くなり、また粒径２０μｍ未満のフェノール樹脂が吹付施工時に発塵により浮遊してしまい、結果として付着性が低下した。

Claims (3)

  1. 　マグネシア質原料を６５質量％以上９５質量％以下、フェノール樹脂を０．５質量％以上１０質量％以下含有し、
    　かつ、粒径２０μｍ未満のマグネシア質原料の含有量が５質量％以上３０質量％以下、粒径２０μｍ未満のフェノール樹脂の含有量が０．３質量％以上９質量％以下であり、
    　「前記粒径２０μｍ未満のマグネシア質原料の含有量／前記粒径２０μｍ未満のフェノール樹脂の含有量」が０．６以上３０以下である熱間補修用吹付材。
  2. 　ピッチを０．５質量％以上１０質量％以下含有する請求項１に記載の熱間補修用吹付材。
  3. 　「前記粒径２０μｍ未満のマグネシア質原料の含有量／前記粒径２０μｍ未満のフェノール樹脂の含有量」が０．６以上２０以下である請求項１又は２に記載の熱間補修用吹付材。
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ES2988274T3 (es) 2024-11-19
AU2018394519A1 (en) 2020-05-14
TWI697469B (zh) 2020-07-01
JP2019119622A (ja) 2019-07-22
EP3733631A1 (en) 2020-11-04
JP6340131B1 (ja) 2018-06-06
EP3733631C0 (en) 2024-08-07
AU2018394519B2 (en) 2020-12-10
EP3733631A4 (en) 2021-09-22
EP3733631B1 (en) 2024-08-07
CN111032596B (zh) 2022-05-06
TW201936549A (zh) 2019-09-16
PL3733631T3 (pl) 2024-11-25

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