WO2004002920A1 - キャスタブル耐火物用粉体組成物及びそれからなるプレミックス材、プレミックス材の施工方法並びにその耐火性硬化体 - Google Patents
キャスタブル耐火物用粉体組成物及びそれからなるプレミックス材、プレミックス材の施工方法並びにその耐火性硬化体 Download PDFInfo
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- WO2004002920A1 WO2004002920A1 PCT/JP2003/008280 JP0308280W WO2004002920A1 WO 2004002920 A1 WO2004002920 A1 WO 2004002920A1 JP 0308280 W JP0308280 W JP 0308280W WO 2004002920 A1 WO2004002920 A1 WO 2004002920A1
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- alumina cement
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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
- C04B35/622—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
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/62665—Flame, plasma or melting treatment
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- 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
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
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- 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
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- 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
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- 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)
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- 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
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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- 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
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
- C04B2235/3873—Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
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- 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
- C04B2235/424—Carbon black
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- 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
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- 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
Definitions
- the present invention relates to a castable refractory powder composition for lining a molten metal container such as a blast furnace gutter, a ladle and a tundish, a premix material thereof, and a premix material, which is applied at room temperature without heating and curing.
- the present invention relates to a curing method and a fire-resistant cured product obtained by the method.
- premix materials which mix with other kneading liquids and deliver them to construction sites, have become widespread.
- Premix materials have new problems such as hardening over time, separation of aggregates during transportation, and floating of water, but (a) compared to conventional cast refractories, (a) the amount of kneading water is more stable and sufficient kneading is possible. (B) Since no kneading process is required, labor at the site can be saved, and there is no generation of dust, and the working environment can be improved. (C) Since the material does not cure at room temperature, there is an advantage that there is no worry about curing problems even if the construction is temporarily suspended. These advantages are behind the spread of premix materials.
- JP-A-4-83764 and JP-A-6-48845 disclose a method of heat-curing a premix material containing a thermosetting curing agent while heating and curing at a temperature of 80 ° C or more. A method is disclosed. While these heat curing methods are used, energy loss and mold Regular by maintenance or the like high construction cost to heat deformation, also due to the rapid de-ice by heating the weakened construction body tissue, strength problems force S when was the decrease.
- JP-A-5-60469 uses alumina cement in a slurry state as a cold-setting binder.
- alumina cement slurry hardens with the passage of time, it cannot be placed and needs to be prepared each time it is applied.
- Japanese Patent Application Laid-Open No. 2000-16843 proposes an alumina cement composition having a remarkably long pot life, a method of spraying the same, and an irregular refractory by such a method. Because the pot life is very long, even after the spraying operation is completed, the amorphous refractories remaining in the equipment can be stored without discarding, and can be used after the next day. Therefore, according to the spraying construction method using the alumina cement composition, cost reduction and labor reduction can be achieved.
- Patent alumina cement composition No. 2000-16843 is 60 to 95 wt% of CaO'2Al 2 O 3, 2CaO'Al 2 O 3 ⁇ Si0 2 of from 5 to 30 weight 0/0, ⁇ Pi 10 weight 0 / It contains alumina cement made of clinker having a crystalline mineral composition of CaO * AI2O3 of 0 or less, and a setting retarder for alumina cement.
- This document uses at least one selected from the group consisting of phosphoric acids, boric acids, ky fluorides, oxycarboxylic acids, polycarboxylic acids, polyoxycarboxylic acids, polyoxyalkylenes and sugars as retarders. Is preferred.
- alumina cement clinker minerals described in this document since a main component CaO'2Al 2 0 3 ⁇ Pi 2CaO'Al2O 3 'Si0 2, is very low hydration activity. Therefore, the hardening retardant composed of an alkaline salt such as sodium tripolyphosphate, sodium citrate, sodium polyacrylate, etc. described in the examples of this reference is used for alumina cement mainly composed of clinker mineral having low hydration activity. although exerts an effective delay effect for the delay effect against the universal alumina cement mainly high CaO'Al 2 0 3 of hydrous activity does not reach 24 hours, it was not sufficient. Purpose of the invention
- an object of the present invention is to provide a powder composition for a castable refractory, which can obtain an alumina cement-containing premix material which retains fluidity for a long time when kneaded with water.
- Another object of the present invention is to provide an alumina cement-containing premix material which retains flowability for a long time.
- Still another object of the present invention is to provide a method of applying such a premix material by changing it to room temperature curability at the time of application.
- Still another object of the present invention is to provide a fire-resistant cured product obtained by subjecting such a premix material to ordinary temperature hardening. Disclosure of the invention
- hydrolysis stopping agent a substance that stops the hydration reaction of alumina cement
- a powder composition for castable refractories containing alumina cement a powder composition for castable refractories containing alumina cement.
- the powder composition for castable refractories of the present invention contains a refractory aggregate, a refractory fine powder, alumina cement, a dispersant, and a powdery hydration terminator of alumina cement.
- a refractory aggregate composed of a substance that exhibits acidity in the form of an aqueous solution, and the amount of the hydration terminator added is such that the pH of the premix material obtained by kneading the powder composition for castable refractories with water is 2 to 7 It is characterized by being adjusted so that
- the premix material of the present invention is obtained by previously kneading a powder composition for castable refractories containing refractory aggregate, refractory fine powder, alumina cement, a dispersant, and a hydration stopper for alumina cement.
- the hydration terminator is acidic in the form of an aqueous solution. Wherein the amount of the hydration terminator is adjusted so that the pH of the premix material is 2 to 7.
- the method for applying the premix material of the present invention is as follows: a powder composition for a castable refractory containing a refractory aggregate, a refractory fine powder, an alumina cement, a dispersant, and a hydration stopping agent for an alumina cement is preliminarily mixed with water. It is characterized in that a premix material is prepared by kneading at a time, a hydration initiator of alumina cement is added and kneaded at the time of applying the premix material, and then the mixture is poured into a mold.
- the hydration terminator It is preferable to use a substance that exhibits acidity in the form of an aqueous solution as the hydration terminator, and it is preferable to adjust the amount of the hydration terminator so that the pH of the premix material is 2 to 7.
- the addition amount of the hydration initiator is 0.02 to 0.5% by mass, with the total of the refractory aggregate, the refractory fine powder and the alumina cement being 100% by mass. / 0 is preferable.
- the refractory hardened body of the present invention is characterized by being obtained by adding and kneading a hydration initiator of alumina cement to the premix material and then kneading the mixture.
- the hydration terminating agent used in the powder composition for castable refractories is oxycarbonic acid and its salts, polyacrylic acid and its derivatives, salts of atalilic acid, chelating agents, condensed phosphates, aluminum phosphate and the like.
- at least one member selected from the group consisting of boric acid is used.
- phosphoric acid may be used as a hydration terminator in addition to the above compounds.
- the alumina cement hydration initiator to be added to the premix material includes alkali metal aluminates, hydroxides, carbonates, nitrites, silicates and borates, and alkali earth metal oxides. It is preferably at least one selected from the group consisting of hydroxides.
- the premix material is passed through a pipe by a pressure pump, a hydration initiator of the alumina cement is added to the premix material in the pipe, and the mixture is kneaded. Preferably, it is poured into a mold.
- the kneading of the premix material and the hydration initiator is preferably performed through a line mixer.
- the number of storage days after production (the number of days the premix material has a flowable flowability) is 5 days or more, and preferably 7 days or more. Therefore, it is preferable that the production of the premix material and the addition of the hydration initiator be more than 5 days Or more than 7 days.
- FIG. 1 (a) is a partial cross-sectional view showing an example of an apparatus (one end of a line mixer is a discharge port) for implementing the premix material applying method of the present invention
- FIG. FIG. 9 is a partial cross-sectional view showing another example of an apparatus (a flexible mixer / hose connected to the end of a line mixer) for implementing the method for applying a premix material of the present invention.
- the powder composition for castable refractories of the present invention contains a refractory aggregate, refractory fine powder, alumina cement, a dispersant, and a small amount of a powdery hydration terminator of alumina cement.
- the powder composition for castable refractories may contain a thickener, a reinforcing material, an anti-explosion-proof material, an acid-proof agent, etc., if necessary.
- the premix material of the present invention is prepared by kneading the powder composition for castable refractories with water in advance and adjusting the workability to allow pouring.
- the alumina cement used in the present invention is preferably one of JIS Class 1, Class 2 and Class 3 in terms of fire resistance, corrosion resistance, high-temperature strength and the like of the obtained construction.
- the content of alumina cement depends on the type of hydration inhibitor.
- the content of alumina cement, refractory aggregate, the total of the refractory fines and Aruminase instrument 100 mass 0/0, 0.1; 12% by mass.
- the content of alumina cement is less than 0.1% by mass, the obtained construction body does not have sufficient de-frame strength, and when the content exceeds 12% by mass, the premix material has poor storage stability and corrosion resistance is deteriorated. I do.
- the more preferable content of the alumina cement is 0.3 to 8% by mass.
- the hydration terminator must be a substance whose aqueous solution exhibits acidity.
- the hydration stopper When the castable refractory powder composition itself is used as a product, the hydration stopper must be in powder form. is there.
- a hydration terminator oxycarboxylic acid and its salt, polyacrylic acid and its derivative, salt of acrylic acid, chelating agent, condensed phosphate, aluminum phosphate and boric acid are preferable, and these are used alone. Or two or more of them can be used in combination.
- the hydration terminating agent does not need to be in the form of powder, but may be phosphoric acid which is usually distributed in a water-containing state.
- examples of oxycarboxylic acid or a salt thereof include dalicholic acid, lactic acid, citric acid, sodium dihydrogen citrate, tartaric acid, malic acid, malonic acid, gluconic acid, base 1 and raw aluminum lactate [commercially available product] as, for example, "Takiseramu GMJ (32 wt% of A1 2 0 3, 45.5 wt% of containing P 2 O 5 lactate ⁇ Pi 4.8 wt%, trade name of Taki Chemical Co., Ltd.)], and the like.
- lactic acid and dalconic acid are liquids and should be added to the premix material.
- the polyacrylic acid derivative is a copolymer of an acrylic acid monomer and another monomer, and the other monomer is selected so as not to adversely affect the water solubility of the polymer.
- the salt of acrylic acid include aluminum acrylate.
- the chelating agent include EDTA.
- the condensed phosphate include sodium acid pyrophosphate, sodium hexametaphosphate, sodium acid hexametaphosphate, sodium pentanopolyphosphate, and the like.
- condensed phosphate and polyacrylic acid are also used as dispersants.
- the added amount is usually about 0.05 to 0.15% by mass, and the pH of the premix material does not become 2 to 7 with such a small amount.
- a preferable addition amount is 0.4% by mass as shown in Example 8 described later.
- the present inventors have found that, even with a condensed phosphate and polyacrylinoleic acid used as a dispersant with a small amount of addition, when the amount of addition is increased so that the pH of the premix material becomes 2 to 7, It has been discovered that the hydration reaction of alumina cement is stopped, and an unexpected effect is obtained in that storage can be continued for as long as 5 days or more.
- the amount of addition of these acidic hydration terminators mainly depends on the acidity of the hydration terminator and the amount of alumina cement in the powder composition for castable refractories. It is necessary to adjust so that Premitsu If the pH of the wood mix exceeds 7, the hydration stopping effect is insufficient and the premix stock has poor storage stability. On the other hand, if the pH of the premix material is less than 2, the premix material tends to be in a pseudo-coagulated state, and its storage stability is also low. This pseudo-coagulation phenomenon is considered to be caused by the direct chemical reaction between the alumina cement and the acid, due to the considerable heat generation. The more preferred pH of the premix material is 3-6.
- the mechanism of action of the acidic hydration terminating agent is considered as follows.
- Alumina cement reacts immediately upon contact with water and elutes Ca 2+ and AF + ions.
- the pH of the water rises, and hydrates of alumina cement precipitate from a certain pH stage.
- Ca 2+ is captured, and the weakly added water suppresses the progress of the hydration reaction of alumina cement.
- it causes gelation of aluminum hydroxide, one of the hydration products of alumina cement.
- the aluminum gel is deposited and coated on the surface of the alumina cement. It is presumed that a small amount of aluminum hydroxide gel is generated.
- the hydration reaction is stopped for at least 5 days after production, and preferably the hydration reaction is stopped for 7 days or more.
- the storage period of the premix material (the number of days having pourable fluidity) is 5 days or more, and preferably 7 days or more. For this reason, there is enough time between production at the factory, storage, transportation to the construction site, and construction at the site.
- Refractory 'I ⁇ raw aggregates include fused alumina, sintered alumina, bauxite, wyanite, andalusite, mullite, chamotte, rhoite, quartzite, aluminum-magnesia spinel, magnesia, zircon, zircon-a, At least one selected from the group consisting of silicon carbide, graphite, pitch and the like can be used, and if necessary, two or more can be used in combination.
- the refractory fine powder at least one selected from the group consisting of fine powders of alumina, amorphous silica, silica, titania, mullite, zirconia, chromia, silicon carbide, carbon, clay and the like can be used. .
- the average particle size of the refractory fine powder is preferably 70 m or less.
- a refractory ultrafine powder of 10 ⁇ m or less, more preferably 1 m or less is used as a part of the refractory fine powder, a premix material having low flow rate and good fluidity can be obtained in combination with a dispersant.
- dispersant examples include condensed phosphates such as sodium hexametaphosphate, sodium acid hexametaphosphate, and sodium ultrapolyphosphate, ⁇ -naphthalene sulfonate formalin condensate, melamine sulfonate formalin condensate, aminosulfonic acid and the like.
- Condensed phosphates such as sodium hexametaphosphate, sodium acid hexametaphosphate, and sodium ultrapolyphosphate
- ⁇ -naphthalene sulfonate formalin condensate melamine sulfonate formalin condensate
- aminosulfonic acid and the like examples include condensed phosphates such as sodium hexametaphosphate, sodium acid hexametaphosphate, and sodium ultrapolyphosphate, ⁇ -naphthalene sulfonate formalin condensate, melamine sulfonate formalin condensate,
- the amount of dispersant added is 100 mass of refractory aggregate, refractory fine powder and alumina cement. / 0 is preferably 0.01 to 1% by mass (outside ratio). If the amount of the dispersant is less than 0.01% by mass or more than 1% by mass, it is difficult to obtain a good dispersion state of the refractory fine powder. Note that the above addition amount does not apply to all dispersants, and the amount of addition force is appropriately changed depending on the type of the dispersant. For example, in the case of condensed phosphate, polyacrylic acid and salts thereof, the amount of addition is usually about 0.05 to 0.15 mass. /. It is.
- the powder composition for castable refractories of the present invention may contain, in addition to the components described above, other components that can be blended in a range that does not impair the preservability of the premix material and the action of the hydration initiator.
- other components that can be blended in a range that does not impair the preservability of the premix material and the action of the hydration initiator.
- an inorganic or metal fiber for improving the strength of the construction body an organic fiber or a foaming agent for preventing steam explosion during drying, an antioxidant such as boron carbide, and the like may be contained.
- the premix material of the present invention may further contain a thickening agent such as a cellulose derivative, gum, or alginate for preventing the separation of the aggregate or the floating of water during transportation.
- the premix material of the present invention is obtained by previously kneading the powder composition for castable refractories with water and adjusting the workability so that the workability can be poured. Become an important factor. Reduce the amount of kneading water within a range that does not impair the fluidity and improve the denseness of the construction body structure by uniformly kneading T JP2003 / 008280
- the amount of kneading water is greatly affected by the specific gravity and porosity of the refractory aggregate and refractory fine powder used, the particle size composition of the refractory composition, and other components. It is preferably about 4.5 to 9% by mass (outer part), more preferably 5 to 8.5% by mass (outer part) based on the mass%. If the mixing water amount is less than 4.5% by mass, the fluidity of the obtained premix material is low, and if it exceeds 9% by mass, there is a tendency for water to float in the premix material and separation of aggregates during transportation.
- the hydration initiator is a substance that restores the hydratability of the stopped alumina cement.
- the hydration initiator is selected from the group consisting of alkali metal aluminates, hydroxides, carbonates, nitrites, silicates and borates, and alkaline earth metal oxides and hydroxides. At least one can be used. It is necessary to determine the type and amount of hydration initiator in accordance with the type and amount of hydration terminator in the premix material.
- the addition amount of the hydration initiator is preferably 0.02 to 0.5% by mass (outside ratio), with the total amount of the refractory aggregate, refractory fine powder and alumina cement being 100% by mass. However, when two or more hydration initiators are used in combination, the total amount shall be 0.02 to 0.5% by mass (outside). If the content is less than 0.02% by mass, the strength is not sufficiently developed, and if the content is more than 0.5% by mass, pseudo-congealing of the material occurs, and it is difficult to perform construction. The more preferable addition amount of the hydration initiator is 0.04 to 0.3 mass. / 0 (outside).
- the hydration initiator can be added in the form of an aqueous solution or slurry.
- the mechanism of action of the hydration initiator is assumed to be as follows. Since the above hydration initiator exhibits an alkaline property, when mixed into the premix material, it changes the water content of the premix material to alkaline. The alkaline water dissolves the hydroxylated aluminum gel coating that coats the alumina cement surface. As a result, a new unreacted alumina cement surface appears, and the alumina cement starts hydration reaction again.
- the method for applying a premix material according to the present invention is characterized in that a hydration initiator of an alumina cement is added to the premix material at the time of application, the mixture is kneaded, and then the premix material is poured into a mold to perform the application. . Hydration of alumina cement to premix material
- the means for adding and kneading the initiator is not particularly limited, and ordinary kneading machines and other means can be used. However, it is preferable to use a line mixer as a kneading means in order to take advantage of the fact that one of the features of the premix material is that kneading on site is unnecessary and that the process can be labor-saving.
- a line mixer is a device that does not have a drive unit, but has a mechanism that disrupts the flow of fluid by the energy of the flowing fluid. For this reason, the line mixer installed in the piping system mixes fluids (for example, different types of liquids, powders, or mixtures thereof) uniformly.
- a static mixer a static mixer, a twisted pipe, a pipe in which different diameter pipes are connected, or the like can be used, but a static mixer is preferable because of its excellent stirring ability.
- a static mixer is a tubular device with a helical mixing element mounted inside, and can mix two or more fluids uniformly by passing through a tube, and is also called a static mixer.
- a preferred example of the static mixer is disclosed in JP-A-2000-356475. Among them, a static mixer having a mixing element having an inner diameter of 40 to 150 mm, an axial length Z of 1.5 to 3 and a number of elements of 6 or more is more preferable.
- the illustrated construction apparatus includes a pipe 5, a pump 3 provided upstream of the pipe 5, a hopper 4 provided on the pump 3, and a hydration initiator injection device 8 provided at a downstream end of the pipe 5.
- a line mixer 9 (having a discharge port 10) provided therein, a metering pump 6 provided upstream of a pipe 18 connected to a hydration initiator injection device 8, and a hydration initiator provided upstream thereof
- a container 7 for storing an aqueous solution or slurry 17.
- a powder composition for castable refractories containing a small amount of alumina cement hydration stop agent is kneaded in advance with water at a place other than the site of use, such as a manufacturing plant, so as to adjust the workability so that it can be poured. .
- the obtained premix material 1 is packed in, for example, a container pack 2 made of Vininole so as not to evaporate moisture, and is stocked. If necessary, the premix material 1 is transported to a construction site for construction. At the time of construction, the premix material 1 is put into the hopper 4, and the inside of the pipe 5 is pressure-fed to the discharge port 10 by the pressure pump 3.
- an aqueous solution or slurry 17 of the hydration initiator is injected into the pipe 5 from the hydration initiator injection device 8 and the metering pump 6 Inject using. While passing through the line mixer 9, the aqueous solution or slurry 17 of the hydration initiator is uniformly kneaded with the premix material 1, and the cold-curable premix material 11 is obtained. The room temperature curable premix material 11 is poured into the mold 13 (the space between the molten metal perm lining 12 and the mold 13 in the illustrated example) from the discharge port 10.
- the pump 3 used in the present invention is not particularly limited, but it is preferable to use a biston type or a squeeze type.
- the hydration initiator injection device 8 is not particularly limited as long as it can inject the aqueous solution or slurry 17 of the hydration initiator into the premix material 1 fed through the pipe 5.
- a so-called nozzle pod that has a built-in ring for dry spraying and has approximately 8 to 16 holes (or slits) that are evenly opened and that is connected to the nozzle and used for water injection.
- the metering pump 6 used to inject the aqueous solution or slurry 17 of the hydration initiator into the pipe 5 is preferably a multiple-type non-pulsating plunger pump or a monopump, and a multiple-type non-pulsating plunger in that high-pressure injection is possible. Pumps are more preferred.
- the injection pressure of the metering pump 6 is preferably 5 kgcm 2 or more.
- the line mixer 9 is installed adjacent to the hydration initiator injection device 8, but the installation position of the line mixer 9 may be changed as appropriate.
- a part of the pipe 5 may extend between the line mixer 9 and the hydration initiator injector 8.
- Fig. 1 (a) shows an example in which one end of the line mixer 9 also serves as the discharge port 10.When the force construction site is narrow and complicated, or when the pouring place is at a high place and there is a restriction on piping management.
- a flexible hose 14 made of rubber or the like may be connected to the line mixer 9 as shown in FIG.
- Table 1 shows the results of measuring the pH of aqueous solutions of various hydration stop agents for alumina cement.
- concentration of the hydration terminator whose pH was measured was as follows.
- the pH of trisodium citrate is also shown for comparison.
- the various hydration stop agents shown in Table 1 were added to the powder composition for castable refractories having the composition shown in Table 2, and 6.5% by mass of water was added to the obtained composition on an outer basis.
- the mixture was kneaded to prepare a premix material.
- the premix obtained is at 25 ⁇ 1 ° C 280 Saved.
- Table 3 shows the relationship between the pH and preservability of the premix material.
- Comparative Example 1 the same hydration terminator (sodium hexametaphosphate + boric acid) was used as in Example 9, but the pH of the premix material was as high as 8 because the amount of the hydration terminator was insufficient.
- the storage days of the premix material were as short as less than 1 day.
- Comparative Example 3 since the phosphoric acid was used as the hydration terminator, the pH of the premix material was lower than 2. Therefore, it is highly probable that a direct acid-base reaction occurred between phosphoric acid and alumina cement, and pseudo-coagulation occurred in a short time with heat generation.
- Various hydration initiators were added to the premix materials of Examples 1 to 9, and the room-temperature curing speed of the premix material with each hydration initiator was examined.
- the premix material was prepared by adding 6.5% by mass of water to a powder composition for castable refractories containing various hydration terminating agents and kneading with a universal mixer. 25 pre-mixed materials obtained 1 After storing at C for 2 days, various hydration initiators were added, kneaded, poured into a mold, allowed to cure, and the curing time was measured. The curing time was the time during which no deformation occurred even when finger pressure was applied to each cured product. Table 4 shows the measurement results. Table 4
- Example 14 Example 15
- Example 16 Premix material
- Example 6 Example ⁇
- Example 8 Example 9 Hydration initiator
- Table 3 Example was added 6.5 mass 0/0 of water castable refractory powder composition for the formulation shown in 1, to produce a pre-mix material 20 tons kneaded by a large vortex mixer.
- the obtained premix material was stocked at room temperature (about 15 to 23 ° C) for 9 days, transported to the construction site of the steel mill, and installed on the blast furnace gutter.
- the premix material 1 is put into the hopper 4, and the inside of the pipe 5 is pressure-fed by the pressure pump 3 and the aqueous solution of sodium aluminate (concentration: 19% by mass) is passed through the hydration initiator injection device 8 provided near the line mixer 9. Of 0.19% by mass (in terms of solid content) was injected. After kneading through a line mixer 9, the obtained cold-curable premix material 11 was poured from a nozzle 10 into a space between a perm lining 12 and a mold 13. The same room temperature-curable premix material 11 was separately applied to a small test formwork, and cured for about 11 hours to obtain a construction. After drying this construction at 110 ° C, Were measured for physical properties. Table 6 shows the measurement results. Table 6
- the premix material manufactured at the factory remote from the construction site was transported to the construction site, where the hydration initiator was added to the premix material, kneaded, and then poured and constructed.
- the method is not limited.
- the premix material may be conveyed to a construction site in the form of a castable refractory powder composition, kneaded with a predetermined amount of water to form a premix material, and the premix material may be applied.
- the premix material of the present invention When the premix material of the present invention is used, it is only necessary to add and knead the hydration initiator on site at the time of construction, so that there is an advantage that the construction time can be spared, and as a result, the work becomes easier.
- the premix material obtained by adding the alumina cement hydration stop agent to the castable refractory powder composition containing alumina cement does not cure for a long time and has a remarkably long pot life. Therefore, it may be left in a kneader or tank for a long time.
- the performance of the refractory made of the premix material of the present invention it is possible to prevent the tissue from becoming brittle due to the rapid dehydration caused by heating.
- Premix If a line mixer is used as a facility for adding and kneading a hydration initiator to the material, it is possible to save labor by one j.
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03738584A EP1535887A1 (en) | 2002-06-28 | 2003-06-30 | Powder composition for castable refractory and premixed material comprising the same, method for applying premixed material and refractory hardened product therefrom |
AU2003246149A AU2003246149A1 (en) | 2002-06-28 | 2003-06-30 | Powder composition for castable refractory and premixed material comprising the same, method for applying premixed material and refractory hardened product therefrom |
CA002491530A CA2491530A1 (en) | 2002-06-28 | 2003-06-30 | Castable refractory powder composition, premixed material prepared therefrom, method for casting premixed material, and hardened refractory body obtained therefrom |
JP2004517326A JP4382662B2 (ja) | 2002-06-28 | 2003-06-30 | プレミックス材の施工方法 |
US10/519,005 US20050239630A1 (en) | 2002-06-28 | 2003-06-30 | Powder composition for castable refractory and premixed material comprising the same, method for applying premixed material and refractory hardene product therefrom |
US12/240,411 US8017058B2 (en) | 2002-06-28 | 2008-09-29 | Castable refractory powder composition, premixed material prepared therefrom, method for casting premixed material, and hardened refractory body obtained therefrom |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2002190229 | 2002-06-28 | ||
JP2002-190229 | 2002-06-28 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10519005 A-371-Of-International | 2003-06-30 | ||
US12/240,411 Division US8017058B2 (en) | 2002-06-28 | 2008-09-29 | Castable refractory powder composition, premixed material prepared therefrom, method for casting premixed material, and hardened refractory body obtained therefrom |
Publications (1)
Publication Number | Publication Date |
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WO2004002920A1 true WO2004002920A1 (ja) | 2004-01-08 |
Family
ID=29996877
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/008280 WO2004002920A1 (ja) | 2002-06-28 | 2003-06-30 | キャスタブル耐火物用粉体組成物及びそれからなるプレミックス材、プレミックス材の施工方法並びにその耐火性硬化体 |
Country Status (8)
Country | Link |
---|---|
US (2) | US20050239630A1 (ja) |
EP (1) | EP1535887A1 (ja) |
JP (1) | JP4382662B2 (ja) |
KR (1) | KR20050034652A (ja) |
CN (1) | CN1308260C (ja) |
AU (1) | AU2003246149A1 (ja) |
CA (1) | CA2491530A1 (ja) |
WO (1) | WO2004002920A1 (ja) |
Cited By (4)
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JP2007039256A (ja) * | 2005-07-29 | 2007-02-15 | Kurosaki Harima Corp | 不定形耐火物の施工方法およびそれに使用するスラリー |
JP2007145618A (ja) * | 2005-11-25 | 2007-06-14 | Taiheiyo Material Kk | 余りモルタル又はコンクリート用固結抑制剤及び余りモルタル又はコンクリートの処理方法 |
JP2008007369A (ja) * | 2006-06-29 | 2008-01-17 | Jfe Refractories Corp | 流し込み材の硬化促進方法およびその流し込み材 |
JP6054488B1 (ja) * | 2015-08-19 | 2016-12-27 | 株式会社山崎工業 | セルフレベリング材スラリー供給装置及び平坦面の形成方法 |
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US9802866B2 (en) * | 2005-06-09 | 2017-10-31 | United States Gypsum Company | Light weight gypsum board |
FR2892717B1 (fr) * | 2005-10-28 | 2008-09-05 | Ecole Nationale Superieure Artes Metiers | Produits cimentaires a surface gelifiee |
JP5132494B2 (ja) * | 2008-09-12 | 2013-01-30 | Jx日鉱日石エネルギー株式会社 | 硫黄固化体製品の型枠装置 |
JP5290125B2 (ja) * | 2008-10-24 | 2013-09-18 | 新日鐵住金株式会社 | 不定形耐火物用結合剤及び不定形耐火物 |
CN101397204B (zh) * | 2008-10-24 | 2011-06-08 | 浙江锦诚耐火材料有限公司 | 一种耐酸耐碱浇注料 |
FR2961807B1 (fr) * | 2010-06-24 | 2013-11-01 | Lafarge Sa | Procede de transport d'une composition hydraulique |
US9090507B2 (en) | 2013-04-18 | 2015-07-28 | Missouri Refractories | Low cement spinel stabilized silicon carbide composite material |
CN103319188A (zh) * | 2013-06-19 | 2013-09-25 | 宜兴兴贝耐火材料制品有限公司 | 抗腐蚀碳化硅耐磨可塑料 |
FR3035399B1 (fr) * | 2015-04-24 | 2019-08-09 | Kerneos | Adjuvant pour composition de ciment ou de beton refractaire, ses utilisations, et compositions de ciment et de beton refractaire |
WO2017067951A1 (en) | 2015-10-20 | 2017-04-27 | Hilti Aktiengesellschaft | Use of a calcium sulfate comprising 2-k mortar system based on aluminous cement in anchoring applications to increase load values and reduce shrinkage |
AU2016342204B2 (en) | 2015-10-20 | 2020-11-19 | Hilti Aktiengesellschaft | Two-component mortar system based on aluminous cement and use thereof |
CN106123602B (zh) * | 2016-08-19 | 2018-02-27 | 郑州东方安彩耐火材料有限公司 | 耐火材料安全浇注生产*** |
CA3050526A1 (en) | 2017-01-25 | 2018-08-02 | Jens Decker | Single additive refractory materials suitable for multiple application methods |
US11267765B2 (en) | 2017-04-07 | 2022-03-08 | Hilti Aktiengesellschaft | Use of amorphous calcium carbonate in a fire-resistant inorganic mortar system based on aluminous cement to increase load values at elevated temperatures |
JP6509416B1 (ja) * | 2017-11-20 | 2019-05-08 | 花王株式会社 | 鋳物製造用構造体 |
CN109970458B (zh) * | 2017-12-28 | 2022-03-01 | 埃肯硅材料(兰州)有限公司 | 一种改性碳质溜槽及其制备方法 |
CN112351964A (zh) | 2018-07-06 | 2021-02-09 | 巴斯夫欧洲公司 | 用于可流动的耐火材料的组合物 |
CN110746195B (zh) * | 2019-08-30 | 2022-04-12 | 山东耀华特耐科技有限公司 | 免醒可塑料生产工艺 |
KR20230131247A (ko) * | 2021-04-07 | 2023-09-12 | 제이에프이 스틸 가부시키가이샤 | 캐스터블 내화물 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06293569A (ja) * | 1993-04-05 | 1994-10-21 | Nippon Steel Corp | 混練耐火物 |
JP2001056184A (ja) * | 1999-08-13 | 2001-02-27 | Shinagawa Refract Co Ltd | 不定形耐火物の流し込み施工方法およびその装置 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0653617B2 (ja) | 1990-07-24 | 1994-07-20 | 品川白煉瓦株式会社 | 熱硬化性樋用流し込み材 |
JPH0560469A (ja) | 1991-08-28 | 1993-03-09 | Kawasaki Refract Co Ltd | 不定形耐火物の施工方法 |
JP2556418B2 (ja) | 1992-07-14 | 1996-11-20 | 大光炉材株式会社 | 不定形耐火材 |
US6409819B1 (en) * | 1998-06-30 | 2002-06-25 | International Mineral Technology Ag | Alkali activated supersulphated binder |
JP4023916B2 (ja) | 1998-07-02 | 2007-12-19 | 電気化学工業株式会社 | アルミナセメント、アルミナセメント組成物、その不定形耐火物、及びそれを用いた吹付施工方法 |
-
2003
- 2003-06-30 US US10/519,005 patent/US20050239630A1/en not_active Abandoned
- 2003-06-30 KR KR1020047021394A patent/KR20050034652A/ko not_active Application Discontinuation
- 2003-06-30 EP EP03738584A patent/EP1535887A1/en not_active Withdrawn
- 2003-06-30 CN CNB038147092A patent/CN1308260C/zh not_active Expired - Fee Related
- 2003-06-30 AU AU2003246149A patent/AU2003246149A1/en not_active Abandoned
- 2003-06-30 CA CA002491530A patent/CA2491530A1/en not_active Abandoned
- 2003-06-30 WO PCT/JP2003/008280 patent/WO2004002920A1/ja active Application Filing
- 2003-06-30 JP JP2004517326A patent/JP4382662B2/ja not_active Expired - Lifetime
-
2008
- 2008-09-29 US US12/240,411 patent/US8017058B2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06293569A (ja) * | 1993-04-05 | 1994-10-21 | Nippon Steel Corp | 混練耐火物 |
JP2001056184A (ja) * | 1999-08-13 | 2001-02-27 | Shinagawa Refract Co Ltd | 不定形耐火物の流し込み施工方法およびその装置 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007039256A (ja) * | 2005-07-29 | 2007-02-15 | Kurosaki Harima Corp | 不定形耐火物の施工方法およびそれに使用するスラリー |
JP4528224B2 (ja) * | 2005-07-29 | 2010-08-18 | 黒崎播磨株式会社 | 不定形耐火物の施工方法およびそれに使用するスラリー |
JP2007145618A (ja) * | 2005-11-25 | 2007-06-14 | Taiheiyo Material Kk | 余りモルタル又はコンクリート用固結抑制剤及び余りモルタル又はコンクリートの処理方法 |
JP2008007369A (ja) * | 2006-06-29 | 2008-01-17 | Jfe Refractories Corp | 流し込み材の硬化促進方法およびその流し込み材 |
JP6054488B1 (ja) * | 2015-08-19 | 2016-12-27 | 株式会社山崎工業 | セルフレベリング材スラリー供給装置及び平坦面の形成方法 |
Also Published As
Publication number | Publication date |
---|---|
JP4382662B2 (ja) | 2009-12-16 |
AU2003246149A1 (en) | 2004-01-19 |
CA2491530A1 (en) | 2004-01-08 |
CN1308260C (zh) | 2007-04-04 |
CN1662472A (zh) | 2005-08-31 |
US8017058B2 (en) | 2011-09-13 |
US20050239630A1 (en) | 2005-10-27 |
US20090032999A1 (en) | 2009-02-05 |
EP1535887A1 (en) | 2005-06-01 |
JPWO2004002920A1 (ja) | 2005-10-27 |
KR20050034652A (ko) | 2005-04-14 |
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