WO2023013284A1 - 焼成炉用の乾式吹付材 - Google Patents
焼成炉用の乾式吹付材 Download PDFInfo
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- WO2023013284A1 WO2023013284A1 PCT/JP2022/025240 JP2022025240W WO2023013284A1 WO 2023013284 A1 WO2023013284 A1 WO 2023013284A1 JP 2022025240 W JP2022025240 W JP 2022025240W WO 2023013284 A1 WO2023013284 A1 WO 2023013284A1
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- calcium
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- 239000000463 material Substances 0.000 title claims abstract description 61
- 238000005507 spraying Methods 0.000 title claims abstract description 46
- 238000010304 firing Methods 0.000 title claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 229
- 239000002245 particle Substances 0.000 claims abstract description 90
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000000203 mixture Substances 0.000 claims abstract description 64
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 41
- 150000007514 bases Chemical class 0.000 claims abstract description 39
- 239000011230 binding agent Substances 0.000 claims abstract description 39
- 239000004568 cement Substances 0.000 claims abstract description 38
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 33
- 239000003513 alkali Substances 0.000 claims abstract description 33
- 239000000292 calcium oxide Substances 0.000 claims abstract description 32
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 32
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 32
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 28
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 22
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 22
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 22
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 22
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 11
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 11
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 11
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 11
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 52
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 36
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 32
- 239000010452 phosphate Substances 0.000 claims description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 17
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 17
- 229910052845 zircon Inorganic materials 0.000 claims description 17
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 17
- 239000007921 spray Substances 0.000 claims description 16
- 239000011362 coarse particle Substances 0.000 claims description 14
- 235000021317 phosphate Nutrition 0.000 abstract description 30
- 238000001035 drying Methods 0.000 abstract description 10
- 229910052681 coesite Inorganic materials 0.000 abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 abstract description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000011156 evaluation Methods 0.000 description 29
- 230000000694 effects Effects 0.000 description 28
- 238000005260 corrosion Methods 0.000 description 26
- 230000007797 corrosion Effects 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 24
- 238000004880 explosion Methods 0.000 description 15
- 229910052878 cordierite Inorganic materials 0.000 description 14
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 14
- 239000011521 glass Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000005299 abrasion Methods 0.000 description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 8
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000010349 pulsation Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000004111 Potassium silicate Substances 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000011449 brick Substances 0.000 description 4
- 239000001506 calcium phosphate Substances 0.000 description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 description 4
- 235000011010 calcium phosphates Nutrition 0.000 description 4
- 239000000378 calcium silicate Substances 0.000 description 4
- 229910052918 calcium silicate Inorganic materials 0.000 description 4
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000004035 construction material Substances 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 description 4
- 229910052912 lithium silicate Inorganic materials 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 description 4
- 235000011009 potassium phosphates Nutrition 0.000 description 4
- 229910052913 potassium silicate Inorganic materials 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 4
- 239000001488 sodium phosphate Substances 0.000 description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052661 anorthite Inorganic materials 0.000 description 3
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 3
- 239000010459 dolomite Substances 0.000 description 3
- 229910000514 dolomite Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910001678 gehlenite Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- F27—FURNACES; KILNS; OVENS; RETORTS
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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
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- C04B35/16—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 silicates other than clay
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
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- F27D1/0003—Linings or walls
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- F27D1/16—Making or repairing linings increasing the durability of linings or breaking away linings
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- 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
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- 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
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Definitions
- the present invention is a dry spraying material for firing furnaces such as incinerators, fluidized bed furnaces, industrial waste kiln treatment furnaces, circulating fluidized bed (CFB) boiler furnaces, cement manufacturing facility furnaces, gasification melting furnaces, and stoker furnaces. Regarding.
- firing furnaces such as incinerators, fluidized bed furnaces, industrial waste kiln treatment furnaces, circulating fluidized bed (CFB) boiler furnaces, cement manufacturing facility furnaces, gasification melting furnaces, and stoker furnaces.
- Patent Document 1 a sprayed material using alumina cement as a binder is known (see Patent Document 1, for example).
- Patent Literature 1 describes that it can be applied to incinerators as well as blast furnace troughs, torpedo trucks, and the like.
- a firing furnace such as an incinerator that heat-treats (burns and incinerates) the materials inside the furnace
- the sprayed body that becomes the furnace wall is subject to physical impacts and erosion reactions from the materials flowing in the furnace.
- the spraying material described in Patent Document 1 is a wet spraying material that is applied to wet spraying construction.
- wet spraying the raw material mixture and water are sufficiently kneaded in advance by a mechanical kneading mechanism such as a mixer, and the kneaded kneaded product is pumped by a pump, and air and a quick-setting agent are applied at or immediately before the nozzle. (Hardening agent) is introduced and sprayed.
- a mechanical kneading mechanism is required and the equipment becomes large-scale.
- wet spraying since the pressure during spraying is high, the reaction force is strong, and only a short nozzle can be used. Therefore, it is necessary for workers to enter the furnace to perform the work, and only cold work can be performed. Moreover, since only a short nozzle can be used, there is also a problem that the application site is limited.
- Patent Document 1 there is a method of using cement (alumina cement, Portland cement, magnesia cement, etc.) as a binder for a spraying material for a kiln.
- cement alumina cement, Portland cement, magnesia cement, etc.
- a hydration reaction increases the strength of the sprayed product, making dehydration difficult, and there is a risk of explosion if the temperature inside the furnace increases. For this reason, a drying process is required after spraying, and there is the problem that the drying process requires a lot of money and requires a long period of stoppage time.
- the problem to be solved by the present invention is to provide a dry spraying material for a firing furnace that does not require a drying process after spraying and can suppress physical impact from objects in the furnace.
- the following dry gunning material for kilns is provided.
- a dry spraying material for a firing furnace having a furnace wall temperature of 1400 ° C. or less The dry spray material comprises a raw material blend, The raw material mixture contains a total of 2% by mass or more and 15% by mass or less of one or more of powdery alkali silicate and powdery alkali phosphate, and magnesium oxide having a particle size of less than 75 ⁇ m; A total of 0.00 of basic compound fine powder of one or more selected from magnesium carbonate, magnesium sulfate, magnesium nitrate, calcium oxide (excluding cement-derived calcium oxide), calcium carbonate, calcium sulfate and calcium nitrate.
- the remaining composition of the raw material mixture is any one of the following (1) to (3), (1) It mainly contains an alumina raw material, and contains at least one of a silica raw material, an alumina-silica raw material and a zircon raw material in addition to the alumina raw material that is mainly contained.
- the raw material mixture contains 1% by mass or more and 10% by mass or less of the SiO 2 component derived from the raw material having a particle size of less than 75 ⁇ m, and 5% by mass and 40% by mass of the Al 2 O 3 component derived from the raw material having a particle size of less than 75 ⁇ m. % or less, dry spraying materials for firing furnaces.
- a dry spraying material for a firing furnace having a furnace wall temperature of 1400 ° C. or less comprises a raw material blend and a liquid binder,
- the liquid binder is one or more selected from liquid alkali silicate and liquid alkali phosphate, and the amount of the liquid binder added is 5% by mass or more and 40% by mass or less
- the raw material mixture is one selected from magnesium oxide, magnesium carbonate, magnesium sulfate, magnesium nitrate, calcium oxide (excluding cement-derived calcium oxide), calcium carbonate, calcium sulfate, and calcium nitrate having a particle size of less than 75 ⁇ m, or Containing 0.1% by mass or more and 5% by mass or less in total of two or more basic compound fine powders, 1 selected from magnesium oxide, magnesium carbonate, magnesium sulfate, magnesium nitrate, calcium oxide (excluding cement-derived calcium oxide), calcium carbonate, calcium s
- the dry spray material contains 1% by mass or more and 10% by mass or less of the SiO 2 component derived from the raw material having a particle size of less than 75 ⁇ m, and 5% by mass and 40% by mass of the Al 2 O 3 component derived from the raw material having a particle size of less than 75 ⁇ m. % or less, dry spraying materials for firing furnaces.
- the "particle size” as used in the present invention refers to the size of the sieve mesh when the raw material particles are separated by sieving.
- a basic compound fine powder that passes through a sieve with a mesh size of 75 ⁇ m, and a basic compound coarse particle with a particle size of 1 mm or more is a basic compound coarse particle that does not pass through a sieve with a mesh size of 1 mm.
- a basic compound fine powder having a particle size of less than 75 ⁇ m, a raw material-derived SiO 2 component having a particle size of less than 75 ⁇ m, and a raw material-derived Al 2 O 3 component having a particle size of less than 75 ⁇ m. reacts to form cordierite, gehlenite or anorthite, improving the strength of the sprayed product.
- an alkali silicate when used, the effect of forming a glass film by the reaction between the alkali silicate and the Al 2 O 3 component derived from the raw material having a particle size of less than 75 ⁇ m and the effect of improving the strength due to the formation of cordierite and the like are combined.
- alkali phosphate when alkali phosphate is used, the alkali phosphate reacts with basic compound fine powder having a particle size of less than 75 ⁇ m to produce magnesium orthophosphate, calcium orthophosphate, etc., which have high refractoriness. improves. This refractory improvement effect and the strength improvement effect due to the formation of cordierite and the like are combined to suppress the physical impact from the objects in the furnace.
- a dry spraying material of one embodiment of the present invention is a dry spraying material for a firing furnace having a furnace wall temperature of 1400° C. or less, and is pneumatically conveyed to a nozzle or just before the nozzle. It consists of a raw material blend.
- a dry spraying material of another embodiment of the present invention (hereinafter referred to as "second embodiment") is a dry spraying material for a firing furnace having a furnace wall temperature of 1400° C. or less, and includes a nozzle or just before the nozzle. It consists of a pneumatically conveyed raw mix and a liquid binder added at or near the nozzle.
- the raw material composition for the dry spraying material of the first embodiment contains one or more of powdery alkali silicate and powdery alkali phosphate as a powdery binder, and the total amount is 2% by mass or more and 15% by mass. % or less and selected from magnesium oxide, magnesium carbonate, magnesium sulfate, magnesium nitrate, calcium oxide (excluding cement-derived calcium oxide), calcium carbonate, calcium sulfate and calcium nitrate having a particle size of less than 75 ⁇ m or Two or more basic compound fine powders are contained in a total amount of 0.1% by mass or more and 5% by mass or less.
- this raw material mixture contains 1% by mass or more and 10% by mass or less of SiO 2 component derived from raw material having a particle size of less than 75 ⁇ m, and 5% by mass of Al 2 O 3 component derived from raw material having a particle size of less than 75 ⁇ m. It contains 40% by mass or less.
- Cordierite (2MgO.2Al 2 O 3.5SiO 2 )
- Gelenite 2CaO.Al 2 O 3.SiO 2
- Anorthite CaO.Al 2 O 3.2SiO 2
- the glass coating is formed mainly by the reaction between the alkali silicate and Al 2 O 3 components derived from raw materials having a particle size of less than 75 ⁇ m in a furnace wall temperature range of 1400° C. or less.
- the effect of forming the glass coating and the effect of improving the strength due to the formation of cordierite or the like are combined to suppress the physical impact from the objects in the furnace.
- the glass film melts, so the above effect cannot be obtained. Therefore, the use of the dry spraying material of the present invention is limited to firing furnaces having a furnace wall temperature of 1400° C. or less.
- the furnace wall temperature is preferably 1200° C. or lower.
- the lower limit of the furnace wall temperature is not particularly limited, and is determined by the lower limit of the firing temperature of the firing furnace.
- alkali phosphate when alkali phosphate is used, magnesium orthophosphate with high refractoriness is produced by mainly reacting alkali phosphate with basic compound fine powder having a particle size of less than 75 ⁇ m in the furnace wall temperature range of 1400° C. or less. , Calcium orthophosphate, etc. are generated, so the fire resistance is improved.
- the effect of improving the fire resistance and the effect of improving the strength due to the formation of cordierite or the like combine to suppress the physical impact from the objects in the furnace.
- the alkali silicate and the alkali phosphate are used in combination, both the effect of forming the glass film and the effect of improving the fire resistance can be obtained.
- the total content of one or more of the powdery alkali silicate and the powdery alkali phosphate is less than 2% by mass, the glass film formation effect and the fire resistance improvement effect described above cannot be obtained. .
- the corrosion resistance and adhesion of the dry-blasted material to the furnace wall are reduced.
- the total content of one or more of powdery alkali silicate and powdery alkali phosphate is preferably 3.5% by mass or more and 10% by mass or less.
- the powdery alkali silicate is typically composed of one or more of powdery sodium silicate, lithium silicate, potassium silicate and calcium silicate.
- Powdered alkali phosphate is typically composed of one or more of powdered sodium phosphate, lithium phosphate, potassium phosphate and calcium phosphate.
- the total content of the basic compound fine powder having a particle size of less than 75 ⁇ m is less than 0.1% by mass, the strength improvement effect due to the formation of cordierite or the like cannot be obtained. On the other hand, if it exceeds 5% by mass, the expansion and contraction will increase and the adhesiveness will decrease.
- the total content of basic compound fine powder having a particle size of less than 75 ⁇ m is preferably 0.2% by mass or more and 3% by mass or less.
- the basic compound fine powder having a particle size of less than 75 ⁇ m is selected from magnesium oxide, magnesium carbonate, magnesium sulfate, magnesium nitrate, calcium oxide (excluding cement-derived calcium oxide), calcium carbonate, calcium sulfate and calcium nitrate having a particle size of less than 75 ⁇ m. is one or two or more.
- magnesium oxide is most preferable from the viewpoint of having a low volatile content and relatively excellent digestion resistance.
- Electro-fused magnesium, heavy-burnt magnesium, light-burnt magnesium, and the like can be used as magnesium oxide.
- the basic compound fine powder having a particle size of less than 75 ⁇ m in the raw material mixture can be contained alone as magnesium oxide fine powder, calcium oxide fine powder, etc., and for example, magnesium oxide and calcium oxide can be combined as calcined dolomite fine powder.
- the total content of basic compound coarse particles with a particle size of 1 mm or more and less than 5 mm in the raw material mixture is limited to 10% by mass or less (including 0). This is because if the content of the basic compound coarse particles having a particle size of 1 mm or more and less than 5 mm exceeds 10% by mass, the expansion and contraction will increase and the adhesive strength will decrease.
- the content of basic compound coarse particles having a particle size of 1 mm or more and less than 5 mm is preferably 5% by mass or less (including 0).
- the raw material mixture of the first embodiment contains powdery alkali silicate and/or alkali phosphate, basic compound fine powder having a particle size of less than 75 ⁇ m, etc., and the remainder is composed of the following (1): to (3).
- It mainly contains an alumina raw material, and contains at least one of a silica raw material, an alumina-silica raw material and a zircon raw material in addition to the alumina raw material that is mainly contained.
- the above (1) is the case where the balance of the raw material mixture mainly contains the alumina raw material, and is particularly suitable for applications requiring high heat resistance.
- the above (2) is a case where the balance of the raw material mixture mainly contains the alumina-silica raw material, and is suitable for applications where the heat resistance requirement is not as high as the above (1), and is effective from the viewpoint of reducing the raw material cost. be.
- the above (3) is the case where the balance of the raw material mixture mainly contains the silicon carbide raw material, and is particularly suitable for applications requiring high wear resistance and corrosion resistance.
- the term "mainly" means that the content of the raw material exceeds 50% by mass in the total amount of 100% by mass of the raw material mixture.
- the remainder of the raw material mixture mainly contains an alumina raw material
- a silica raw material, an alumina-silica raw material, and a zircon raw material including at least one of This is to ensure both the SiO 2 component and the Al 2 O 3 component derived from raw materials, which will be described later. That is, in (1) above, the Al 2 O 3 component derived from the raw material is secured mainly by the alumina raw material, and at least one of the silica raw material, alumina-silica raw material, and zircon (ZrO 2 ⁇ SiO 2 ) raw material is used as the raw material.
- the raw material mixture in addition to the silicon carbide raw material mainly contained, contains an alumina-silica raw material, or an alumina raw material, a silica raw material, and a zircon raw material. and at least one of That is, in the above (3), in addition to the silicon carbide raw material that is mainly included, the alumina-silica raw material is included, and in addition to the silicon carbide raw material that is mainly included, at least one of the alumina raw material, the silica raw material, and the zircon raw material is included.
- both the raw material-derived SiO 2 component and the Al 2 O 3 component are secured by the alumina-silica raw material
- the raw material-derived Al 2 O 3 component is secured by the alumina raw material
- the raw material-derived SiO 2 component is secured by at least one of the silica raw material and the zircon raw material.
- the remainder includes refractory raw materials other than the above refractory raw materials, powdery binders other than powdered alkali silicate and powdered alkali phosphate (alumina cement, etc.), hardening modifiers (sulfate, slaked lime, etc.), Explosion prevention agents (organic fibers, etc.) and the like may be included as appropriate.
- powdery binders other than powdered alkali silicate and powdered alkali phosphate (alumina cement, etc.)
- hardening modifiers sulfate, slaked lime, etc.
- Explosion prevention agents organic fibers, etc.
- the content of cement is preferably 2% by mass or less (including 0).
- the raw material mixture contains 1% by mass or more and 10% by mass or less of the SiO 2 component derived from the raw material having a particle size of less than 75 ⁇ m, and 5 Al 2 O 3 components derived from the raw material having a particle size of less than 75 ⁇ m. It contains 40% by mass or less. If the content of the SiO 2 component derived from the raw material having a particle size of less than 75 ⁇ m is less than 1% by mass, the aforementioned effect of improving the strength due to the formation of cordierite or the like cannot be obtained. On the other hand, when it exceeds 10% by mass, a low-melting substance is formed and the corrosion resistance is lowered.
- the content of the Al 2 O 3 component derived from the raw material having a particle size of less than 75 ⁇ m is less than 5% by mass, the above-described effect of forming a glass film and improving fire resistance cannot be obtained.
- it exceeds 40% by mass the amount of water added during the spraying process is increased, which impairs the compactness of the sprayed product and reduces the corrosion resistance.
- the content of the SiO 2 component derived from the raw material with a particle size of less than 75 ⁇ m is preferably 3% by mass or more and 7% by mass or less, and the content of the Al 2 O 3 component derived from the raw material with a particle size of less than 75 ⁇ m is 25% by mass or more.
- the SiO 2 component and Al 2 O 3 component derived from raw materials with a particle size of less than 75 ⁇ m are refractory raw materials with a particle size of less than 75 ⁇ m (alumina raw material, silica raw material, alumina-silica raw material, etc.) and other raw materials (hardening modifiers, etc.).
- SiO 2 component and Al 2 O 3 component as main components or impurity components contained in
- SiO 2 component and Al 2 O 3 as main components or impurity components contained in
- SiO 2 component and Al 2 O 3 as main components or impurity components contained in alkali silicate and alkali phosphate having a particle size of less than 75 ⁇ m
- SiO 2 component and Al 2 O 3 component as impurity components contained in the basic compound fine powder having a particle size of less than 75 ⁇ m.
- the raw material mixture is air-conveyed to the nozzle or just before the nozzle, water is added at the nozzle or just before the nozzle, and the mixture is sprayed into the kiln.
- the amount of water to be added may be appropriately determined so that the spraying softness of the dry spraying material made of the raw material mixture is within an appropriate range. It is more than 15 mass % or less.
- the water content of the raw material mixture is preferably 1% by mass or less.
- the water content of the raw material mixture is measured by the loss-on-drying method specified in JIS K 0068. That is, the sample is dried by heating at about 105° C. until it reaches a constant weight, the weight loss after drying is measured, and the weight is taken as the water content.
- a liquid binder one or more selected from liquid alkali silicate and liquid alkali phosphate
- It may be added, or water and a liquid binder may be used in combination.
- the dry spray material of the second embodiment consists of a raw material mixture that is pneumatically conveyed to the nozzle or just before the nozzle, and a liquid binder that is added to the nozzle or just before the nozzle.
- the liquid binder is one or more selected from liquid alkali silicate and liquid alkali phosphate.
- a powdery binder one or two selected from powdery alkali silicate and powdery alkali phosphate is added to the raw material mixture pneumatically conveyed to the nozzle or just before the nozzle.
- a liquid binder one selected from liquid alkali silicate and liquid alkali phosphate or 2 or more
- a liquid binder one selected from liquid alkali silicate and liquid alkali phosphate or 2 or more
- the first embodiment and the second embodiment differ in the form of the binder, but they share the following basic technical idea for solving the problems.
- the raw material mixture pneumatically conveyed to the nozzle or just before the nozzle contains 0.1% by mass or more and 5% by mass or less of basic compound fine powder having a particle size of less than 75 ⁇ m.
- a liquid binder one or more selected from liquid alkali silicate and liquid alkali phosphate
- the dry spraying material of the second embodiment is composed of a raw material mixture and a liquid binder, and contains 1% by mass or more and 10% by mass of SiO2 component derived from raw materials having a particle size of less than 75 ⁇ m. 5% by mass or less and 40% by mass or less of Al 2 O 3 component derived from raw materials having a particle size of less than 75 ⁇ m.
- Each content is the same as in the first embodiment, and the preferred range of each content is also the same as in the first embodiment.
- the components of the liquid binder are also the same as those of the first embodiment. Therefore, even in the second embodiment, in the temperature range of the furnace wall temperature of 1400 ° C.
- the basic compound fine powder with a particle size of less than 75 ⁇ m, the SiO 2 component derived from the raw material with a particle size of less than 75 ⁇ m, and the raw material with a particle size of less than 75 ⁇ m By reacting with the Al 2 O 3 component, cordierite (2MgO.2Al 2 O 3.5SiO 2 ), galenite (2CaO.Al 2 O 3.SiO 2 ) or anorthite (CaO.Al 2 O 3 . 2SiO 2 ) to improve the strength of the sprayed product.
- the glass coating is formed mainly by the reaction between the alkali silicate and Al 2 O 3 components derived from raw materials having a particle size of less than 75 ⁇ m in a furnace wall temperature range of 1400° C. or less.
- the effect of forming the glass coating and the effect of improving the strength due to the formation of cordierite or the like are combined to suppress the physical impact from the objects in the furnace.
- the alkali phosphate when used as a binder, the alkali phosphate mainly reacts with the basic compound fine powder having a particle size of less than 75 ⁇ m in the furnace wall temperature range of 1400° C. or less, resulting in high refractory.
- Fire resistance is improved because magnesium orthophosphate, calcium orthophosphate, etc. are formed.
- the effect of improving the fire resistance and the effect of improving the strength due to the formation of cordierite or the like combine to suppress the physical impact from the objects in the furnace.
- the alkali silicate and the alkali phosphate are used together, both the effect of forming the glass film and the effect of improving the fire resistance described above can be obtained.
- the amount of the liquid binder to be added is 5% by mass or more and 40% by mass or less. If the amount added is less than 5% by mass, the glass film-forming effect and fire resistance improving effect described above cannot be obtained. In addition, corrosion resistance and adhesion deteriorate due to lack of bonding. On the other hand, when it exceeds 40% by mass, a low-melting substance is formed and the corrosion resistance is lowered.
- the amount of liquid binder added is preferably 8% by mass or more and 30% by mass or less.
- addition amount refers to the addition amount of the external coating with respect to the total amount of 100% by mass of the raw material mixture.
- the liquid binder is one or more of liquid alkali silicate and liquid alkali phosphate.
- the liquid alkali silicate is typically composed of one or more of liquid sodium silicate, lithium silicate, potassium silicate and calcium silicate.
- Liquid alkali phosphate is typically composed of one or more of liquid sodium phosphate, lithium phosphate, potassium phosphate and calcium phosphate.
- the liquid binder contains water in the solid content of alkali silicate and alkali phosphate, and the solid content concentration is adjusted in the range of approximately 5% by mass or more and 50% by mass or less based on 100% by mass of the liquid binder. .
- the liquid binder added to the nozzle or immediately before the nozzle is preferably added from one conveying route, but may be added from a plurality of conveying routes. is the total amount added from multiple conveying routes.
- liquid binders having different solid concentrations may be added through different conveying routes.
- water may be added from a conveying route different from the conveying route of the liquid binder, and in this case, the liquid binder shall include the water added from the separate conveying route.
- the total content of basic compound coarse particles having a particle size of 1 mm or more and less than 5 mm in the raw material mixture is limited to 10% by mass or less (including 0), preferably 5% by mass or less (0 including).
- the remaining composition of the raw material mixture is any one of the following (1) to (3) as in the first embodiment. (1) It mainly contains an alumina raw material, and contains at least one of a silica raw material, an alumina-silica raw material and a zircon raw material in addition to the alumina raw material that is mainly contained. (2) It contains mainly alumina-silica raw materials.
- the balance may include refractory raw materials other than the above refractory raw materials, powdery binders (alumina cement, etc.), hardening modifiers (sulfate, slaked lime, etc.), explosion inhibitors (organic fibers, etc.), etc. as appropriate.
- powdery binders alumina cement, etc.
- hardening modifiers sulfate, slaked lime, etc.
- explosion inhibitors organic fibers, etc.
- the content of cement is preferably 2% by mass or less (including 0).
- a powdery binder one or more of powdery alkali silicate and powdery alkali phosphate is added to the raw material mixture within a range that does not impair the effects of the present invention. ) may contain.
- the dry spray material of the second embodiment contains 1% by mass or more and 10% by mass or less of the SiO 2 component derived from the raw material having a particle size of less than 75 ⁇ m and the Al 2 O 3 component derived from the raw material having a particle size of less than 75 ⁇ m. 5% by mass and 40% by mass or less. If the content of the SiO 2 component derived from the raw material having a particle size of less than 75 ⁇ m is less than 1% by mass, the aforementioned effect of improving the strength due to the formation of cordierite or the like cannot be obtained. On the other hand, when it exceeds 10% by mass, a low-melting substance is formed and the corrosion resistance is lowered.
- the content of the Al 2 O 3 component derived from the raw material having a particle size of less than 75 ⁇ m is less than 5% by mass, the above-described effect of forming a glass film and improving fire resistance cannot be obtained.
- it exceeds 40% by mass the amount of water in the liquid binder added to the nozzle or just before the nozzle increases, which impairs the compactness of the sprayed product and lowers the corrosion resistance.
- the SiO 2 component and Al 2 O 3 component derived from raw materials with a particle size of less than 75 ⁇ m are refractory raw materials with a particle size of less than 75 ⁇ m (alumina raw material, silica raw material, alumina-silica raw material, etc.) and other raw materials (hardening modifiers, etc.).
- alumina raw material, silica raw material, alumina-silica raw material, etc. alumina raw material, silica raw material, alumina-silica raw material, etc.
- other raw materials hardening modifiers, etc.
- the water content of the raw material mixture is 1% by mass or less from the viewpoint of suppressing the clogging of the raw material mixture that is air-conveyed to the nozzle or just before the nozzle from adhering to the inner surface of the conveying pipe. is preferably In the second embodiment, the addition amount of the liquid binder and the solid content concentration are appropriately adjusted so that the spraying softness of the dry spraying material is within an appropriate range.
- Table 1 shows examples according to the first embodiment
- Table 2 shows comparative examples. Abrasion resistance, corrosion resistance, adhesiveness and explosion resistance were evaluated for the dry sprayed material of each example shown in Tables 1 and 2, and a comprehensive evaluation was made based on these evaluation results.
- alkali silicate (powder) means one or more of powdery sodium silicate, lithium silicate, potassium silicate and calcium silicate
- alkali phosphate (powder)" is one or more of powdery sodium phosphate, lithium phosphate, potassium phosphate and calcium phosphate.
- the evaluation method and evaluation criteria for each evaluation item are as follows. ⁇ Abrasion resistance> After kneading with a water amount assuming an appropriate spraying softness, the molded sample was fired at a firing temperature (see Table 1) assuming the furnace wall temperature of the firing furnace, and then the wear amount was evaluated by sandblasting. A wear amount of less than 10 cc was evaluated as ⁇ (excellent), a wear amount of 10 cc or more and less than 15 cc was evaluated as ⁇ (good), and a wear amount of 15 cc or more was evaluated as x (poor).
- Adhesion strength was measured as an indicator of adhesiveness. Adhesive strength was measured by the following method assuming hot construction. A brick is placed in an atmosphere of 700° C., and a cylindrical metal frame is set thereon. A dry spraying material (construction material) mixed with an appropriate amount of water is cast into the metal frame, and after a certain period of time, the shear strength between the construction material and the brick is measured while the metal frame is set. In Table 1, the shear strength of Example 1 is indexed as 100. When this index was 110 or more, it was evaluated as ⁇ (excellent);
- Examples 1-24 are dry spray materials within the scope of the present invention.
- the overall evaluation of these was ⁇ (excellent) or ⁇ (good), and good evaluations were obtained for all of wear resistance, corrosion resistance, adhesiveness and explosion resistance.
- Examples 10 to 14 and 16 to 18 are dry-type sprayed materials in which each content is within the preferred range described above.
- the overall evaluation was ⁇ (excellent), which was a better evaluation than the other examples.
- Example 13 calcined dolomite fine powder having a particle size of less than 75 ⁇ m was blended in the raw material mixture, and magnesium oxide and calcium oxide were compounded.
- Transportability slight pulsation occurred in Example 18, in which the water content of the raw material mixture exceeded 1% by mass, but no pulsation occurred in Example 11, in which the water content was 1% by mass or less. .
- Comparative Example 1 is an example in which the content of alkali silicate (powder) is small, and the evaluation of wear resistance, corrosion resistance and adhesiveness was x (poor).
- Comparative Example 2 is an example in which the content of alkali silicate (powder) is large, and the evaluation of corrosion resistance was x (poor).
- Comparative Example 3 is an example that does not contain basic compound fine powder (magnesium oxide fine powder) having a particle size of less than 75 ⁇ m, and was evaluated as x (poor) in wear resistance.
- Comparative Example 4 is an example in which the content of basic compound fine powder (magnesium oxide fine powder) having a particle size of less than 75 ⁇ m is large, and the adhesiveness was evaluated as x (poor).
- Comparative Example 5 is an example in which the content of basic compound coarse particles (magnesium oxide coarse particles) having a particle size of 1 mm or more and less than 5 mm is large, and the adhesion was evaluated as x (poor).
- Comparative Example 6 is an example in which the content of the SiO 2 component derived from the raw material having a particle size of less than 75 ⁇ m is small, and the abrasion resistance was evaluated as x (poor).
- Comparative Example 7 is an example in which the content of the SiO 2 component derived from the raw material having a particle size of less than 75 ⁇ m is large, and the corrosion resistance was evaluated as x (poor).
- Comparative Example 8 is an example in which the content of the Al 2 O 3 component derived from the raw material having a particle size of less than 75 ⁇ m is small, and the abrasion resistance was evaluated as x (poor).
- Comparative Example 9 is an example in which the content of the Al 2 O 3 component derived from the raw material having a particle size of less than 75 ⁇ m is large, and the corrosion resistance and adhesion were evaluated as x (poor).
- Comparative Example 10 is an example in which the firing temperature is high assuming the temperature of the furnace wall of the firing furnace, and the wear resistance evaluation is x (poor).
- Comparative Example 11 is an example in which the content of alumina cement is large, and the evaluation of explosion resistance was x (poor).
- Table 3 shows examples according to the second embodiment
- Table 4 shows comparative examples. Abrasion resistance, corrosion resistance, adhesiveness and explosion resistance were evaluated for the dry sprayed material of each example shown in Tables 3 and 4, and a comprehensive evaluation was made based on these evaluation results.
- "alkali silicate (liquid)” means one or more of liquid sodium silicate, lithium silicate, potassium silicate and calcium silicate
- "alkali phosphate (liquid)” )” is one or more of liquid sodium phosphate, lithium phosphate, potassium phosphate and calcium phosphate.
- the evaluation method and evaluation criteria for each evaluation item are as follows. ⁇ Abrasion resistance> The dry sprayed material of each example was kneaded, and the formed sample was fired at a firing temperature (see Table 1) that assumed the furnace wall temperature of the firing furnace, and then sandblasted to evaluate the amount of wear. A wear amount of less than 10 cc was evaluated as ⁇ (excellent), a wear amount of 10 cc or more and less than 15 cc was evaluated as ⁇ (good), and a wear amount of 15 cc or more was evaluated as x (poor).
- ⁇ Corrosion resistance> The dry sprayed material of each example is kneaded, molded into a crucible shape, and fired at a firing temperature (see Table 1) that assumes the temperature of the furnace wall of the firing furnace. After heating for 12 hours at the assumed firing temperature, the corroded state was confirmed. Synthetic slag containing 60% by mass of CaO, 10% by mass of MgO, 10% by mass of K 2 O, and 20% by mass of P 2 O 5 was used as the corrosive agent. The maximum erosion area of each example was measured, and a relative value with Example 27 as 100 was obtained. The smaller the relative value, the better the corrosion resistance. When this relative value was less than 100, it was evaluated as ⁇ (excellent);
- Adhesion strength was measured as an indicator of adhesiveness. Adhesive strength was measured by the following method assuming hot construction. A brick is placed in an atmosphere of 700° C., and a cylindrical metal frame is set thereon. The kneaded dry spraying material (construction material) is cast into the metal frame, and after a certain period of time, the shear strength between the construction material and the brick is measured while the metal frame is set. In Table 2, the shear strength of Example 21 is indexed as 100. When this index was 110 or more, it was evaluated as ⁇ (excellent);
- Examples 31-54 are dry spray materials within the scope of the present invention.
- the overall evaluation of these was ⁇ (excellent) or ⁇ (good), and good evaluations were obtained for all of wear resistance, corrosion resistance, adhesiveness and explosion resistance.
- Examples 40 to 44 and 46 to 48 are dry-type sprayed materials in which each content is within the preferred ranges described above.
- the overall evaluation was ⁇ (excellent), which was a better evaluation than the other examples.
- Example 33 calcined dolomite fine powder having a particle size of less than 75 ⁇ m was blended in the raw material mixture, and magnesium oxide and calcium oxide were mixedly contained.
- Transportability slight pulsation occurred in Example 48, in which the water content of the raw material mixture exceeded 1% by mass, but no pulsation occurred in Example 41, in which the water content was 1% by mass or less. .
- Comparative Example 31 is an example in which the amount of alkali silicate (liquid) added is small, and the evaluation of wear resistance, corrosion resistance and adhesiveness was x (poor).
- Comparative Example 32 is an example in which the amount of alkali silicate (liquid) added is large, and the evaluation of corrosion resistance was x (poor).
- Comparative Example 33 is an example that does not contain basic compound fine powder (magnesium oxide fine powder) having a particle size of less than 75 ⁇ m, and was evaluated as x (poor) in wear resistance.
- Comparative Example 34 is an example in which the content of basic compound fine powder (magnesium oxide fine powder) having a particle size of less than 75 ⁇ m is large, and the adhesiveness was evaluated as x (poor).
- Comparative Example 35 is an example in which the content of basic compound coarse particles (magnesium oxide coarse particles) having a particle size of 1 mm or more and less than 5 mm is large, and the adhesion was evaluated as x (poor).
- Comparative Example 36 is an example in which the content of the SiO 2 component derived from the raw material having a particle size of less than 75 ⁇ m is small, and the abrasion resistance was evaluated as x (poor).
- Comparative Example 37 is an example in which the content of the SiO 2 component derived from the raw material having a particle size of less than 75 ⁇ m is large, and the corrosion resistance was evaluated as x (poor).
- Comparative Example 38 is an example in which the content of the Al 2 O 3 component derived from the raw material having a particle size of less than 75 ⁇ m is small, and the abrasion resistance was evaluated as x (poor).
- Comparative Example 39 is an example in which the content of the Al 2 O 3 component derived from the raw material having a particle size of less than 75 ⁇ m is large, and the corrosion resistance and adhesion were evaluated as x (poor).
- Comparative Example 40 is an example in which the firing temperature is high assuming the temperature of the furnace wall of the firing furnace, and the wear resistance was evaluated as x (poor).
- Comparative Example 41 is an example in which the content of alumina cement is large, and the evaluation of explosion resistance was x (poor).
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Abstract
Description
炉壁温度が1400℃以下の焼成炉用の乾式吹付材であって、
前記乾式吹付材は原料配合物からなり、
前記原料配合物は、粉末状の珪酸アルカリ及び粉末状のリン酸アルカリのうちの1種又は2種以上を合計で2質量%以上15質量%以下含有すると共に、粒径75μm未満の酸化マグネシウム、炭酸マグネシウム、硫酸マグネシウム、硝酸マグネシウム、酸化カルシウム(セメント由来の酸化カルシウムを除く)、炭酸カルシウム、硫酸カルシウム及び硝酸カルシウムから選択される1種又は2種以上である塩基性化合物微粉を合計で0.1質量%以上5質量%以下含有し、
前記原料配合物中における粒径1mm以上5mm未満の酸化マグネシウム、炭酸マグネシウム、硫酸マグネシウム、硝酸マグネシウム、酸化カルシウム(セメント由来の酸化カルシウムを除く)、炭酸カルシウム、硫酸カルシウム及び硝酸カルシウムから選択される1種又は2種以上である塩基性化合物粗粒の含有量が合計で10質量%以下(0を含む)であると共に、セメントの含有量が5質量%以下(0を含む)であり、
前記原料配合物の残部の構成は、次の(1)から(3)のいずれかであり、
(1)主としてアルミナ原料を含有し、当該主として含まれるアルミナ原料以外に、シリカ原料、アルミナ-シリカ原料及びジルコン原料のうちの少なくとも一種を含む。
(2)主としてアルミナ-シリカ原料を含有する。
(3)主として炭化珪素原料を含有し、当該主として含まれる炭化珪素原料以外に、アルミナ-シリカ原料を含み、又は、アルミナ原料と、シリカ原料及びジルコン原料の少なくとも一方と、を含む。
当該原料配合物中に、粒径75μm未満の原料由来のSiO2成分を1質量%以上10質量%以下含有すると共に、粒径75μm未満の原料由来のAl2O3成分を5質量%40質量%以下含有する、焼成炉用の乾式吹付材。
炉壁温度が1400℃以下の焼成炉用の乾式吹付材であって、
前記乾式吹付材は原料配合物と、液状結合剤とからなり、
前記液状結合剤は、液状の珪酸アルカリ及び液状のリン酸アルカリから選択される1種又は2種以上であって、当該液状結合剤の添加量は5質量%以上40質量%以下であり、
前記原料配合物は、粒径75μm未満の酸化マグネシウム、炭酸マグネシウム、硫酸マグネシウム、硝酸マグネシウム、酸化カルシウム(セメント由来の酸化カルシウムを除く)、炭酸カルシウム、硫酸カルシウム及び硝酸カルシウムから選択される1種又は2種以上である塩基性化合物微粉を合計で0.1質量%以上5質量%以下含有し、
前記原料配合物中における粒径1mm以上5mm未満の酸化マグネシウム、炭酸マグネシウム、硫酸マグネシウム、硝酸マグネシウム、酸化カルシウム(セメント由来の酸化カルシウムを除く)、炭酸カルシウム、硫酸カルシウム及び硝酸カルシウムから選択される1種又は2種以上である塩基性化合物粗粒の含有量が合量で10質量%以下(0を含む)であると共に、セメントの含有量が5質量%以下(0を含む)であり、
前記原料配合物の残部の構成は、次の(1)から(3)のいずれかであり、
(1)主としてアルミナ原料を含有し、当該主として含まれるアルミナ原料以外に、シリカ原料、アルミナ-シリカ原料及びジルコン原料のうちの少なくとも一種を含む。
(2)主としてアルミナ-シリカ原料を含有する。
(3)主として炭化珪素原料を含有し、当該主として含まれる炭化珪素原料以外に、アルミナ-シリカ原料を含み、又は、アルミナ原料と、シリカ原料及びジルコン原料の少なくとも一方と、を含む。
当該乾式吹付材中に、粒径75μm未満の原料由来のSiO2成分を1質量%以上10質量%以下含有すると共に、粒径75μm未満の原料由来のAl2O3成分を5質量%40質量%以下含有する、焼成炉用の乾式吹付材。
(1)主としてアルミナ原料を含有し、当該主として含まれるアルミナ原料以外に、シリカ原料、アルミナ-シリカ原料及びジルコン原料のうちの少なくとも一種を含む。
(2)主としてアルミナ-シリカ原料を含有する。
(3)主として炭化珪素原料を含有し、当該主として含まれる炭化珪素原料以外に、アルミナ-シリカ原料を含み、又は、アルミナ原料と、シリカ原料及びジルコン原料の少なくとも一方と、を含む。
上記(2)は原料配合物の残部に主としてアルミナ-シリカ原料を含有する場合であり、耐熱性の要求が上記(1)ほど高くない用途に好適であって原料コストを低減する観点から有効である。
上記(3)は原料配合物の残部に主として炭化珪素原料を含有する場合であり、特に耐摩耗性及び耐食性の要求が高い用途に好適である。
ここで、「主として」とは原料配合物の総量100質量%中に占める割合で、その原料の含有量が50質量%を超えることをいう。
一方、原料配合物の残部に主としてアルミナ-シリカ原料を含有する上記(2)の場合、当該主として含まれるアルミナ-シリカ原料以外の耐火原料を含む必要性はない。すなわち、上記(2)では、主として含まれるアルミナ-シリカ原料によって原料由来のSiO2成分とAl2O3成分とを共に確保することができるからである。
他方、原料配合物の残部に主として炭化珪素原料を含有する上記(3)の場合、当該主として含まれる炭化珪素原料以外に、アルミナ-シリカ原料を含み、又は、アルミナ原料と、シリカ原料及びジルコン原料の少なくとも一方と、を含む。すなわち、上記(3)では、主として含まれる炭化珪素原料以外に、アルミナ-シリカ原料を含む場合と、主として含まれる炭化珪素原料以外に、アルミナ原料とシリカ原料及びジルコン原料の少なくとも一方とを含む場合とがあり、前者の場合は、アルミナ-シリカ原料によって原料由来のSiO2成分とAl2O3成分とを共に確保し、後者の場合は、アルミナ原料によって原料由来のAl2O3成分を確保すると共に、シリカ原料及びジルコン原料の少なくとも一方によって原料由来のSiO2成分を確保している。
なお、第1実施形態においては、本発明の効果を損なわない範囲で、ノズル又はノズル直前で液状結合剤(液状の珪酸アルカリ及び液状のリン酸アルカリから選択される1種又は2種以上)を添加してもよく、水と液状結合剤を併用して添加してもよい。
また、第2実施形態においてノズル又はノズル直前で添加する液状結合剤は1つの搬送経路から添加するのが好ましいが、複数の搬送経路から添加してもよく、この場合、液状結合剤の添加量は複数の搬送経路から添加された合量となる。このとき、固形分濃度の異なる液状結合剤を異なる搬送経路から添加してもよい。さらには、液状結合剤の搬送経路とは別の搬送経路から水を添加してもよく、この場合、液状結合剤は別の搬送経路から添加された水を含めたものとする。
(1)主としてアルミナ原料を含有し、当該主として含まれるアルミナ原料以外に、シリカ原料、アルミナ-シリカ原料及びジルコン原料のうちの少なくとも一種を含む。
(2)主としてアルミナ-シリカ原料を含有する。
(3)主として炭化珪素原料を含有し、当該主として含まれる炭化珪素原料以外に、アルミナ-シリカ原料を含み、又は、アルミナ原料と、シリカ原料及びジルコン原料の少なくとも一方と、を含む。
なお、残部には上記の耐火原料以外の耐火原料や、粉末状結合剤(アルミナセメント等)、硬化調整剤(硫酸塩、消石灰等)、爆裂防止剤(有機繊維等)などを適宜含み得る。ただし、セメントを多量に含有すると、上述の通り乾燥時の爆裂が起こりやすくなるので、セメントの含有量は5質量%以下(0を含む。)に制限する。セメントの含有量は2質量%以下(0を含む。)であることが好ましい。なお、第2実施形態においては、本発明の効果を損なわない範囲で、原料配合物中に粉末状結合剤(粉末状の珪酸アルカリ及び粉末状のリン酸アルカリのうちの1種又は2種以上)を含有してもよい。
表1及び表2に示す各例の乾式吹付材について、耐摩耗性、耐食性、接着性及び耐爆裂性を評価し、これらの評価結果に基づき総合評価を行った。なお、表1及び表2において、「珪酸アルカリ(粉末)」とは、粉末状の珪酸ソーダ、珪酸リチウム、珪酸カリウム及び珪酸カルシウムのうちの1種又は2種以上であり、「リン酸アルカリ(粉末)」とは、粉末状のリン酸ソーダ、リン酸リチウム、リン酸カリウム及びリン酸カルシウムのうちの1種又は2種以上である。
<耐摩耗性>
適切な吹付軟度を想定した水量で混錬し、成形した試料を焼成炉の炉壁温度を想定した焼成温度(表1参照)で焼成した後、サンドブラストで摩耗量を評価した。
摩耗量が10cc未満の場合を◎(優良)、10cc以上15cc未満の場合を○(良好)、15cc以上の場合を×(不良)とした。
適切な吹付軟度を想定した水量で混練し、るつぼ形状に成形し、焼成炉の炉壁温度を想定した焼成温度(表1参照)で焼成した後、るつぼに侵食剤を30g入れ、さらに上述の炉壁温度を想定した焼成温度で12時間加熱し、侵食状態を確認した。侵食剤としては、CaO:60質量%、MgO:10質量%、K2O:10質量%、P2O5:20質量%の合成スラグを用いた。各例の最大溶損面積を測定し、実施例7を100とした相対値を求めた。この相対値が小さいほど耐食性に優れるということである。
この相対値が100未満の場合を◎(優良)、100以上120未満の場合を〇(良好)、120以上の場合を×(不良)とした。
接着性を表す指標として接着強度を測定した。接着強度は熱間施工を想定し次の方法で測定した。700℃の雰囲気中にれんがを置き、その上に筒状の金枠をセットする。この金枠内に適量の水と混練した乾式吹付材(施工材)を鋳込んで一定時間後に、金枠をセットしたまま施工材とれんがとのせん断強度を測定する。表1では、実施例1のせん断強度を100として指数化して示した。
この指数が110以上の場合を◎(優良)、100以上110未満の場合を〇(良好)、100未満の場合を×(不良)とした。
適切な吹付軟度を想定した水量で混練し、成形した試料を1000℃の雰囲気に投入し、爆裂の程度を評価した。
爆裂なし及び微亀裂なしの場合を◎(優良)、爆裂はないが微亀裂があった場合を○(良好)、爆裂した場合を×(不良)とした。
全ての評価が◎の場合を◎(優良)、×がなくいずれか1つでも○がある場合を○(良好)、いずれか1つでも×がある場合を×(不良)とした。
搬送性については、原料配合物の含有水分量が1質量%を超えている実施例18ではわずかに脈動が生じたが、含有水分量が1質量%以下の実施例11では脈動は生じなかった。
比較例2は、珪酸アルカリ(粉末状)の含有量が多い例であり、耐食性の評価が×(不良)となった。
比較例3は、粒径75μm未満の塩基性化合物微粉(酸化マグネシウム微粉)を含有していない例であり、耐摩耗性の評価が×(不良)となった。
比較例4は、粒径75μm未満の塩基性化合物微粉(酸化マグネシウム微粉)の含有量が多い例であり、接着性の評価が×(不良)となった。
比較例5は、粒径1mm以上5mm未満の塩基性化合物粗粒(酸化マグネシウム粗粒)の含有量が多い例であり、接着性の評価が×(不良)となった。
比較例6は、粒径75μm未満の原料由来のSiO2成分の含有量が少ない例であり、耐摩耗性の評価が×(不良)となった。
比較例7は、粒径75μm未満の原料由来のSiO2成分の含有量が多い例であり、耐食性の評価が×(不良)となった。
比較例8は、粒径75μm未満の原料由来のAl2O3成分の含有量が少ない例であり、耐摩耗性の評価が×(不良)となった。
比較例9は、粒径75μm未満の原料由来のAl2O3成分の含有量が多い例であり、耐食性及び接着性の評価が×(不良)となった。
比較例10は、焼成炉の炉壁温度を想定した焼成温度が高い例であり、耐摩耗性の評価が×(不良)となった。
比較例11は、アルミナセメントの含有量が多い例であり、耐爆裂性の評価が×(不良)となった。
表3及び表4に示す各例の乾式吹付材について、耐摩耗性、耐食性、接着性及び耐爆裂性を評価し、これらの評価結果に基づき総合評価を行った。なお、表3及び表4において、「珪酸アルカリ(液状)」とは、液状の珪酸ソーダ、珪酸リチウム、珪酸カリウム及び珪酸カルシウムのうちの1種又は2種以上であり、「リン酸アルカリ(液状)」とは、液状のリン酸ソーダ、リン酸リチウム、リン酸カリウム及びリン酸カルシウムのうちの1種又は2種以上である。
<耐摩耗性>
各例の乾式吹付材を混錬し、成形した試料を焼成炉の炉壁温度を想定した焼成温度(表1参照)で焼成した後、サンドブラストで摩耗量を評価した。
摩耗量が10cc未満の場合を◎(優良)、10cc以上15cc未満の場合を○(良好)、15cc以上の場合を×(不良)とした。
各例の乾式吹付材を混練し、るつぼ形状に成形し、焼成炉の炉壁温度を想定した焼成温度(表1参照)で焼成した後、るつぼに侵食剤を30g入れ、さらに上述の炉壁温度を想定した焼成温度で12時間加熱し、侵食状態を確認した。侵食剤としては、CaO:60質量%、MgO:10質量%、K2O:10質量%、P2O5:20質量%の合成スラグを用いた。各例の最大溶損面積を測定し、実施例27を100とした相対値を求めた。この相対値が小さいほど耐食性に優れるということである。
この相対値が100未満の場合を◎(優良)、100以上120未満の場合を〇(良好)、120以上の場合を×(不良)とした。
接着性を表す指標として接着強度を測定した。接着強度は熱間施工を想定し次の方法で測定した。700℃の雰囲気中にれんがを置き、その上に筒状の金枠をセットする。この金枠内に混練した乾式吹付材(施工材)を鋳込んで一定時間後に、金枠をセットしたまま施工材とれんがとのせん断強度を測定する。表2では、実施例21のせん断強度を100として指数化して示した。
この指数が110以上の場合を◎(優良)、100以上110未満の場合を〇(良好)、100未満の場合を×(不良)とした。
各例の乾式吹付材を混練し、成形した試料を1000℃の雰囲気に投入し、爆裂の程度を評価した。
爆裂なし及び微亀裂なしの場合を◎(優良)、爆裂はないが微亀裂があった場合を○(良好)、爆裂した場合を×(不良)とした。
全ての評価が◎の場合を◎(優良)、×がなくいずれか1つでも○がある場合を○(良好)、いずれか1つでも×がある場合を×(不良)とした。
搬送性については、原料配合物の含有水分量が1質量%を超えている実施例48ではわずかに脈動が生じたが、含有水分量が1質量%以下の実施例41では脈動は生じなかった。
比較例32は、珪酸アルカリ(液状)の添加量が多い例であり、耐食性の評価が×(不良)となった。
比較例33は、粒径75μm未満の塩基性化合物微粉(酸化マグネシウム微粉)を含有量していない例であり、耐摩耗性の評価が×(不良)となった。
比較例34は、粒径75μm未満の塩基性化合物微粉(酸化マグネシウム微粉)の含有量が多い例であり、接着性の評価が×(不良)となった。
比較例35は、粒径1mm以上5mm未満の塩基性化合物粗粒(酸化マグネシウム粗粒)の含有量が多い例であり、接着性の評価が×(不良)となった。
比較例36は、粒径75μm未満の原料由来のSiO2成分の含有量が少ない例であり、耐摩耗性の評価が×(不良)となった。
比較例37は、粒径75μm未満の原料由来のSiO2成分の含有量が多い例であり、耐食性の評価が×(不良)となった。
比較例38は、粒径75μm未満の原料由来のAl2O3成分の含有量が少ない例であり、耐摩耗性の評価が×(不良)となった。
比較例39は、粒径75μm未満の原料由来のAl2O3成分の含有量が多い例であり、耐食性及び接着性の評価が×(不良)となった。
比較例40は、焼成炉の炉壁温度を想定した焼成温度が高い例であり、耐摩耗性の評価が×(不良)となった。
比較例41は、アルミナセメントの含有量が多い例であり、耐爆裂性の評価が×(不良)となった。
Claims (6)
- 炉壁温度が1400℃以下の焼成炉用の乾式吹付材であって、
前記乾式吹付材は原料配合物からなり、
前記原料配合物は、粉末状の珪酸アルカリ及び粉末状のリン酸アルカリのうちの1種又は2種以上を合計で2質量%以上15質量%以下含有すると共に、粒径75μm未満の酸化マグネシウム、炭酸マグネシウム、硫酸マグネシウム、硝酸マグネシウム、酸化カルシウム(セメント由来の酸化カルシウムを除く)、炭酸カルシウム、硫酸カルシウム及び硝酸カルシウムから選択される1種又は2種以上である塩基性化合物微粉を合計で0.1質量%以上5質量%以下含有し、
前記原料配合物中における粒径1mm以上5mm未満の酸化マグネシウム、炭酸マグネシウム、硫酸マグネシウム、硝酸マグネシウム、酸化カルシウム(セメント由来の酸化カルシウムを除く)、炭酸カルシウム、硫酸カルシウム及び硝酸カルシウムから選択される1種又は2種以上である塩基性化合物粗粒の含有量が合計で10質量%以下(0を含む)であると共に、セメントの含有量が5質量%以下(0を含む)であり、
前記原料配合物の残部の構成は、次の(1)から(3)のいずれかであり、
(1)主としてアルミナ原料を含有し、当該主として含まれるアルミナ原料以外に、シリカ原料、アルミナ-シリカ原料及びジルコン原料のうちの少なくとも一種を含む。
(2)主としてアルミナ-シリカ原料を含有する。
(3)主として炭化珪素原料を含有し、当該主として含まれる炭化珪素原料以外に、アルミナ-シリカ原料を含み、又は、アルミナ原料と、シリカ原料及びジルコン原料の少なくとも一方と、を含む。
当該原料配合物中に、粒径75μm未満の原料由来のSiO2成分を1質量%以上10質量%以下含有すると共に、粒径75μm未満の原料由来のAl2O3成分を5質量%40質量%以下含有する、焼成炉用の乾式吹付材。 - 炉壁温度が1400℃以下の焼成炉用の乾式吹付材であって、
前記乾式吹付材は原料配合物と、液状結合剤とからなり、
前記液状結合剤は、液状の珪酸アルカリ及び液状のリン酸アルカリから選択される1種又は2種以上であって、当該液状結合剤の添加量は5質量%以上40質量%以下であり、
前記原料配合物は、粒径75μm未満の酸化マグネシウム、炭酸マグネシウム、硫酸マグネシウム、硝酸マグネシウム、酸化カルシウム(セメント由来の酸化カルシウムを除く)、炭酸カルシウム、硫酸カルシウム及び硝酸カルシウムから選択される1種又は2種以上である塩基性化合物微粉を合計で0.1質量%以上5質量%以下含有し、
前記原料配合物中における粒径1mm以上5mm未満の酸化マグネシウム、炭酸マグネシウム、硫酸マグネシウム、硝酸マグネシウム、酸化カルシウム(セメント由来の酸化カルシウムを除く)、炭酸カルシウム、硫酸カルシウム及び硝酸カルシウムから選択される1種又は2種以上である塩基性化合物粗粒の含有量が合量で10質量%以下(0を含む)であると共に、セメントの含有量が5質量%以下(0を含む)であり、
前記原料配合物の残部の構成は、次の(1)から(3)のいずれかであり、
(1)主としてアルミナ原料を含有し、当該主として含まれるアルミナ原料以外に、シリカ原料、アルミナ-シリカ原料及びジルコン原料のうちの少なくとも一種を含む。
(2)主としてアルミナ-シリカ原料を含有する。
(3)主として炭化珪素原料を含有し、当該主として含まれる炭化珪素原料以外に、アルミナ-シリカ原料を含み、又は、アルミナ原料と、シリカ原料及びジルコン原料の少なくとも一方と、を含む。
当該乾式吹付材中に、粒径75μm未満の原料由来のSiO2成分を1質量%以上10質量%以下含有すると共に、粒径75μm未満の原料由来のAl2O3成分を5質量%40質量%以下含有する、焼成炉用の乾式吹付材。 - 前記塩基性化合物微粉は酸化マグネシウムである、請求項1又は2に記載の焼成炉用の乾式吹付材。
- 前記粉末状の珪酸アルカリ及び粉末状のリン酸アルカリのうちの1種又は2種以上の含有量が合計で3.5質量%以上10質量%以下である、請求項1に記載の焼成炉用の乾式吹付材。
- 前記液状結合剤の添加量が8質量%以上30質量%以下である、請求項2に記載の焼成炉用の乾式吹付材。
- 前記原料配合物の含有水分量が1質量%以下である、請求項1から5のいずれか一項に記載の焼成炉用の乾式吹付材。
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