JP2022077378A - Dry spray material for firing furnace - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 34
- 239000007921 spray Substances 0.000 title claims abstract description 34
- 238000010304 firing Methods 0.000 title claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 60
- 229910052580 B4C Inorganic materials 0.000 claims abstract description 25
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 16
- 239000010452 phosphate Substances 0.000 claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 5
- 239000000292 calcium oxide Substances 0.000 claims abstract description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 24
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 4
- 230000003628 erosive effect Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000011156 evaluation Methods 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000009970 fire resistant effect Effects 0.000 description 7
- 239000004568 cement Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 238000010276 construction Methods 0.000 description 5
- 230000002950 deficient Effects 0.000 description 5
- 238000004901 spalling Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 2
- 229910052912 lithium silicate Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- HXNZTJULPKRNPR-UHFFFAOYSA-N borinine Chemical compound B1=CC=CC=C1 HXNZTJULPKRNPR-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229940098458 powder spray Drugs 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Furnace Housings, Linings, Walls, And Ceilings (AREA)
Abstract
Description
本発明は、焼却炉、流動床炉、産業廃棄物キルン処理炉、循環流動層（ＣＦＢ）ボイラ用炉、セメント製造設備用炉、ガス化溶融炉、ストーカ炉等の焼成炉用の乾式吹付材に関する。 The present invention is a dry spray material for incinerators, fluidized bed furnaces, industrial waste kiln treatment furnaces, circulating fluidized bed (CFB) boiler furnaces, cement manufacturing equipment furnaces, gasification melting furnaces, stoker furnaces and other firing furnaces. Regarding.
従来、結合剤としてアルミナセメントを適用した吹付材が知られている（例えば、特許文献１参照）。特許文献１には、その用途として高炉樋、混銑車等のほかにも焼却炉に適用できる旨が記載されている。 Conventionally, a spraying material to which alumina cement is applied as a binder is known (see, for example, Patent Document 1). Patent Document 1 describes that it can be applied to an incinerator in addition to a blast furnace gutter, a torpedo wagon, and the like.
焼却炉のように炉内物を熱処理（焼成・焼却）する焼成炉において、その炉壁となる吹付施工体は、炉内で流動している炉内物から物理的な衝撃や侵食反応を受けやすいという問題がある。 In a firing furnace that heat-treats (fires and incinerates) the contents of the furnace like an incinerator, the sprayed construction body that becomes the furnace wall receives physical impact and erosion reaction from the inside of the furnace that is flowing in the furnace. There is a problem that it is easy.
本発明者らは、焼成炉用の吹付材として、結合剤としてアルミナセメントを適用した乾式吹付材を検討したが、吹付施工体の損傷が激しく実用化できなかった。 The present inventors have studied a dry-type spraying material to which alumina cement is applied as a binder as a spraying material for a firing furnace, but the sprayed body is severely damaged and cannot be put into practical use.
本発明が解決しようとする課題は、焼成炉用の乾式吹付材において、炉内物からの物理的な衝撃や侵食反応を抑制し、耐用を向上させることにある。 An object to be solved by the present invention is to suppress physical impact and erosion reaction from the inside of a dry spray material for a firing furnace and improve the durability.
本発明の一観点によれば、次の焼成炉用の乾式吹付材が提供される。
炉壁温度が１４００℃以下の焼成炉用の乾式吹付材であって、
粉末状の珪酸アルカリ及びリン酸アルカリのうちの１種又は２種以上を合計で０．２質量％以上１０質量％以下、炭化硼素を０．３質量％以上５質量％以下、残部に主として、アルミナ原料、シリカ原料、アルミナ－シリカ質原料、炭化珪素原料、マグネシア原料、マグネシア－カルシア質原料、及びこれらの原料の少なくとも１種を含む使用後耐火物原料から選択される１種又は２種以上を含有し、
当該乾式吹付材の総量１００質量％中に、粒径７５μｍ未満の原料由来のＳｉＯ２成分を７質量％以上含有する、焼成炉用の乾式吹付材。
According to one aspect of the present invention, a drywall spray material for the next firing furnace is provided.
A drywall spray material for firing furnaces with a furnace wall temperature of 1400 ° C or less.
A total of 0.2% by mass or more and 10% by mass or less of one or two or more of powdered alkali silicate and alkali phosphate, 0.3% by mass or more and 5% by mass or less of boron carbide, mainly in the balance. One or more selected from post-use refractory raw materials including alumina raw materials, silica raw materials, alumina-silicic raw materials, silicon carbide raw materials, magnesia raw materials, magnesia-calcia raw materials, and at least one of these raw materials. Contains,
A dry-type spray material for a firing furnace, which contains 7% by mass or more of a SiO 2 component derived from a raw material having a particle size of less than 75 μm in a total amount of 100% by mass of the dry-type spray material.
本発明によれば、詳細は後述するが、主として粒径７５μｍ未満の原料由来のＳｉＯ２成分と珪酸アルカリ又はリン酸アルカリとの反応によりガラス被膜を形成し、さらに、炭化硼素の表面とガラス被膜とが反応して硼珪酸ガラスを生成することで、原料粒子同士（炭化硼素と他の耐火原料）の結合が強くなり、しかも、高い硬度を有する炭化硼素が残存するため、炉内物からの物理的な衝撃や侵食反応を抑制し、耐用を向上させることができる。 According to the present invention, the details will be described later, but a glass film is formed mainly by the reaction between the SiO 2 component derived from a raw material having a particle size of less than 75 μm and an alkali silicate or an alkali phosphate, and further, the surface of boron carbide and the glass film. By reacting with and to form borosilicate glass, the bonds between the raw material particles (boron carbide and other fire-resistant raw materials) become stronger, and boron carbide with high hardness remains, so from the inside of the furnace. It can suppress physical impact and erosion reaction and improve durability.
本発明の乾式吹付材は、炉壁温度が１４００℃以下の焼成炉用の乾式吹付材であって、粉末状の珪酸アルカリ及びリン酸アルカリのうちの１種又は２種以上を合計で０．２質量％以上１０質量％以下、炭化硼素を０．３質量％以上５質量％以下含有し、当該乾式吹付材の総量１００質量％中に、粒径７５μｍ未満の原料由来のＳｉＯ２成分を７質量％以上含有することを特徴的な構成要件としている。以下、この特徴的な構成要件による作用効果を説明する。 The dry spray material of the present invention is a dry spray material for a firing furnace having a furnace wall temperature of 1400 ° C. or less, and one or more of powdered alkali silicate and alkali phosphate are used in total of 0. Containing 2% by mass or more and 10% by mass or less, and 0.3% by mass or more and 5% by mass or less of boron carbide, 7 SiO 2 components derived from a raw material having a particle size of less than 75 μm are contained in 100% by mass of the total amount of the dry spray material. It is a characteristic constituent requirement that it contains more than mass%. Hereinafter, the action and effect of this characteristic constituent requirement will be described.
炉壁温度１４００℃以下という温度領域において、主として粒径７５μｍ未満の原料由来のＳｉＯ２成分と、珪酸アルカリ又はリン酸アルカリ由来のアルカリ成分とが反応し、ガラス被膜を形成する。さらに、炭化硼素の表面とガラス被膜とが反応して硼珪酸ガラスを生成し、他の耐火原料と炭化硼素とが強固に接着する。炭化硼素とガラス被膜との反応は炭化硼素粒子の表面のみであるため、吹付施工体中には反応せず残存した炭化硼素が存在する。したがって、粒子同士（炭化硼素と他の耐火原料）の結合が強くなり、しかも、高い硬度を有する炭化硼素が残存するため、吹付施工体の耐摩耗性向上に寄与する。これにより、炉内物からの物理的な衝撃及び侵食反応による吹付施工体の損傷を低減することができる。
なお、１４００℃を超える温度領域では、ガラス被膜が溶融するので上述の効果は得られない。そのため、本発明の乾式吹付材の用途は、炉壁温度が１４００℃以下の焼成炉用に限定している。炉壁温度は１２００℃以下であることが好ましい。炉壁温度の下限は特に限定されず、その焼成炉の焼成温度の下限により決まるが、ガラス被膜生成による効果を確実に得る点から概ね８００℃以上であることが好ましい。
In the temperature range of the furnace wall temperature of 1400 ° C. or lower, the SiO 2 component mainly derived from a raw material having a particle size of less than 75 μm reacts with an alkali component derived from an alkali silicate or an alkali phosphate to form a glass film. Further, the surface of boron carbide reacts with the glass film to form borosilicate glass, and other fire-resistant raw materials and boron carbonized bond are firmly adhered to each other. Since the reaction between the boron carbide and the glass coating is only on the surface of the boron carbide particles, there is residual carbonized boron that does not react in the sprayed body. Therefore, the bonds between the particles (boron carbide and other fire-resistant raw materials) become stronger, and boron carbide having high hardness remains, which contributes to the improvement of wear resistance of the sprayed body. As a result, it is possible to reduce damage to the sprayed construction body due to physical impact from the inside of the furnace and erosion reaction.
In the temperature range exceeding 1400 ° C., the glass film melts, so that the above-mentioned effect cannot be obtained. Therefore, the use of the drywall spray material of the present invention is limited to a firing furnace having a furnace wall temperature of 1400 ° C. or lower. 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, but it is preferably about 800 ° C. or higher from the viewpoint of surely obtaining the effect of forming the glass film.
珪酸アルカリ及び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０．２質量％未満であるとガラス被膜生成による効果が得られない。一方、１０質量％を超えると、低融物を生成して耐食性が低下する。珪酸アルカリ及びリン酸アルカリのうちの１種又は２種以上の含有量は合計で１質量％以上５質量％以下であることが好ましい。
ここで、珪酸アルカリは、典型的には珪酸ソーダ、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種以上からなる。またリン酸アルカリは、典型的にはリン酸ソーダ、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種以上からなる。
If the total content of one or more of the alkali silicate and the alkali phosphate is less than 0.2% by mass, the effect of forming the glass film cannot be obtained. On the other hand, if it exceeds 10% by mass, a low melt is produced and the corrosion resistance is lowered. The total content of one or more of the alkali silicate and the alkali phosphate is preferably 1% by mass or more and 5% by mass or less.
Here, the alkali silicate typically comprises one or more of sodium silicate, lithium silicate, potassium silicate and calcium silicate. Further, the alkali phosphate is typically composed of one or more of sodium phosphate, lithium phosphate, potassium phosphate and calcium phosphate.
炭化硼素の含有量が０．３質量％未満であると、残存する炭化硼素が少なくなり上述の耐摩耗性向上効果が得られない。また炭化硼素の含有量が５質量％超であると、低融物を生成して耐食性が低下すると共に粒子同士（炭化硼素と他の耐火原料）の結合が強くなり過ぎて耐スポーリング性が低下する。さらにコストが高くなるという問題もある。炭化硼素の含有量は０．５質量％以上３質量％以下であることが好ましい。
また、炭化硼素の粒度構成は、粒径０．５ｍｍ未満が５０質量％以上であることが好ましい。粒径０．５ｍｍ未満が５０質量％以上であることにより、吹付施工体中に炭化硼素が万遍なく分散されるため耐摩耗性をさらに向上させることができる。
When the content of boron carbide is less than 0.3% by mass, the amount of boron carbide remaining is small and the above-mentioned effect of improving wear resistance cannot be obtained. If the content of boron carbide is more than 5% by mass, low melt is generated and the corrosion resistance is lowered, and the bonds between the particles (boron carbonized and other refractory raw materials) become too strong and the spalling resistance is improved. descend. There is also the problem of higher costs. The content of boron carbide is preferably 0.5% by mass or more and 3% by mass or less.
Further, it is preferable that the particle size composition of boron carbide is 50% by mass or more when the particle size is less than 0.5 mm. When the particle size of less than 0.5 mm is 50% by mass or more, the boron carbide is evenly dispersed in the sprayed body, so that the wear resistance can be further improved.
本発明の乾式吹付材は、上述のとおり粉末状の珪酸アルカリ及び／又はリン酸アルカリと、炭化硼素を含むが、その残部は、主として、アルミナ原料、シリカ原料、アルミナ－シリカ質原料、炭化珪素原料、マグネシア原料、マグネシア－カルシア質原料、及びこれらの原料の少なくとも１種を含む使用後耐火物原料から選択される１種又は２種以上の耐火原料からなる。なお、残部として挙げた上記の耐火原料は、残部の「主として」であり、残部には上記の耐火原料以外の耐火原料や、珪酸アルカリ及びリン酸アルカリ以外の結合剤（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、アルミナセメントを多量に含有すると水和物が多量に生成することによって、乾燥時の爆裂が起こりやすくなるので、アルミナセメントの含有量は１０質量％以下（０を含む。）であることが好ましく、５質量％以下（０を含む。）であることがより好ましい。 As described above, the dry spray material of the present invention contains powdered alkali silicate and / or alkali phosphate and boron carbide, the remainder of which is mainly alumina raw material, silica raw material, alumina-silicic raw material, silicon carbide. It comprises one or more refractory raw materials selected from post-use refractory raw materials including raw materials, magnesia raw materials, magnesia-silicic raw materials, and at least one of these raw materials. The above-mentioned fire-resistant raw material mentioned as the balance is "mainly" of the balance, and the balance includes fire-resistant raw materials other than the above-mentioned fire-resistant raw materials, binders other than alkali silicate and alkali phosphate (alumina cement, etc.), and hardening. A modifier (sulfate, slaked lime, etc.), an explosion inhibitor (organic fiber, etc.) and the like may be appropriately contained. However, if a large amount of alumina cement is contained, a large amount of hydrate is generated, which tends to cause explosion during drying. Therefore, the content of alumina cement may be 10% by mass or less (including 0). It is preferably 5% by mass or less (including 0), more preferably.
このような乾式吹付材の総量１００質量％中の、粒径７５μｍ未満の原料由来のＳｉＯ２成分の含有量が７質量％未満であると、上述のガラス被膜生成による効果及び耐摩耗性向上効果が得られない。粒径７５μｍ未満の原料由来のＳｉＯ２成分含有量の上限は、ガラス被膜生成という観点からは特に限定する必要はないが、吹付施工体の性状のバランスを考慮すると概ね４０質量％以下とすることができる。また、粒径７５μｍ未満の原料由来のＳｉＯ２成分含有量の好ましい範囲は、１５質量％以上３５質量％以下である。
ここで、粒径７５μｍ未満の原料由来のＳｉＯ２成分は、粒径７５μｍ未満の耐火原料（炭化硼素、アルミナ原料、アルミナ－シリカ質原料、シリカ質原料等）及びその他原料（硬化調整剤等）に含まれる主成分又は不純物成分としてのＳｉＯ２成分、並びに粒径７５μｍ未満の珪酸アルカリ及びリン酸アルカリに含まれる主成分又は不純物成分としてのＳｉＯ２成分の合量であり、これは乾式吹付材の原料配合により特定することができる。
When the content of the SiO 2 component derived from the raw material having a particle size of less than 75 μm is less than 7% by mass in the total amount of 100% by mass of the drywall spray material, the effect of forming the glass film and the effect of improving the wear resistance are improved. Cannot be obtained. The upper limit of the content of the SiO 2 component derived from the raw material having a particle size of less than 75 μm is not particularly limited from the viewpoint of forming a glass film, but it should be approximately 40% by mass or less in consideration of the balance of the properties of the sprayed body. Can be done. Further, the preferable range of the SiO 2 component content derived from the raw material having a particle size of less than 75 μm is 15% by mass or more and 35% by mass or less.
Here, the SiO 2 component derived from a raw material having a particle size of less than 75 μm includes a fire-resistant raw material having a particle size of less than 75 μm (borin dioxide, an alumina raw material, an alumina-silicic raw material, a siliceous raw material, etc.) and other raw materials (curing modifier, etc.). It is the total amount of the SiO 2 component as the main component or the impurity component contained in the above, and the SiO 2 component as the main component or the impurity component contained in the alkali silicate and the alkali phosphate having a particle size of less than 75 μm, which is a dry spray material. It can be specified by the composition of raw materials.
本発明の焼成炉用の乾式吹付材は、乾式吹付施工方法によって焼成炉へ吹付施工される。乾式吹付施工方法とは周知のとおり、吹付ノズルの先端部において乾粉状の吹付材（乾式吹付材）に水を添加して吹き付ける施工方法である。その添加水量は、乾式吹付材の吹付軟度が適切な範囲となるように適宜決定すればよいが、乾式吹付材の総量１００質量％に対して外掛けで概ね１０質量％以上１５質量％以下である。 The dry-type spraying material for a firing furnace of the present invention is sprayed onto a firing furnace by a dry-type spraying method. As is well known, the dry spray construction method is a construction method in which water is added to a dry powder spray material (dry spray material) at the tip of a spray nozzle and sprayed. The amount of added water may be appropriately determined so that the spray softness of the drywall spray material is within an appropriate range, but is approximately 10% by mass or more and 15% by mass or less with respect to the total amount of 100% by mass of the drywall spray material. Is.
表１に示す各例の乾式吹付材について、耐摩耗性、耐食性及び耐スポーリング性を評価し、これらの評価結果に基づき総合評価を行った。また、実施例８と比較例１については実炉試験に供した。なお、表１において、「珪酸アルカリ」とは、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」とは、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。 The drywall spray materials of each example shown in Table 1 were evaluated for wear resistance, corrosion resistance and spalling resistance, and a comprehensive evaluation was performed based on these evaluation results. Further, Example 8 and Comparative Example 1 were subjected to an actual furnace test. In Table 1, "alkali silicate" is one or more of sodium silicate, lithium silicate, potassium silicate and calcium silicate, and "alkali phosphate" is sodium phosphate and phosphoric acid. One or more of lithium, potassium phosphate and calcium phosphate.
各評価項目の評価方法及び評価基準は以下のとおりである。
＜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未満の場合を〇（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。
The evaluation methods and evaluation criteria for each evaluation item are as follows.
<Abrasion resistance>
The sample was kneaded with an amount of water assuming an appropriate spray softness, and the molded sample was fired at a firing temperature (see Table 1) assuming the furnace wall temperature of the firing furnace, and then the amount of wear was evaluated by sandblasting.
When the amount of wear was less than 10 cc, it was evaluated as 〇 (excellent), when it was 10 cc or more and less than 15 cc, it was evaluated as Δ (good), and when it was 15 cc or more, it was evaluated as × (defective).
＜耐食性＞
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３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未満の場合を〇（優良）、１００以上１２０未満の場合を△（良好）、１２０以上の場合を×（不良）とした。
<Corrosion resistance>
After kneading with an amount of water assuming appropriate spray softness, forming into a crucible shape, and firing at a firing temperature (see Table 1) assuming the furnace wall temperature of the firing furnace, 30 g of an erosion agent is added to the crucible, and further described above. It was heated for 12 hours at a firing temperature assuming the furnace wall temperature of the crucible, and the erosion state was confirmed. As the erosion agent, synthetic slag having CaO: 60% by mass, MgO: 10% by mass, K2O: 10% by mass, and P2O 5 : 20 % by mass was used. The maximum melting area of each example was measured, and a relative value was obtained with Example 3 as 100. The smaller this relative value is, the better the corrosion resistance is.
When the relative value is less than 100, it is evaluated as 〇 (excellent), when it is 100 or more and less than 120, it is evaluated as Δ (good), and when it is 120 or more, it is evaluated as × (poor).
＜耐スポーリング性＞
適切な吹付軟度を想定した水量で混練し、成形した試料を焼成炉の炉壁温度を想定した焼成温度（表１参照）の雰囲気に１５分、空冷１５分を１０回繰り返し、亀裂の度合いにより評価した。
亀裂無し又は亀裂幅が１ｍｍ以内の場合を○（優良）、亀裂幅が１ｍｍ超２ｍｍ以下の場合を△（良好）、亀裂幅が２ｍｍ超の場合を×（不良）とした。
<Spalling resistance>
Knead the sample with an amount of water assuming an appropriate spraying softness, and repeat 10 times for 15 minutes and 15 minutes of air cooling in an atmosphere of firing temperature (see Table 1) assuming the furnace wall temperature of the firing furnace, and the degree of cracking. Evaluated by.
The case where there was no crack or the crack width was within 1 mm was evaluated as ◯ (excellent), the case where the crack width was more than 1 mm and 2 mm or less was evaluated as Δ (good), and the case where the crack width was more than 2 mm was evaluated as × (poor).
＜総合評価＞
全ての評価が○の場合を〇（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。
<Comprehensive evaluation>
When all the evaluations were ○, it was evaluated as 〇 (excellent), when there was no × and any one had Δ, it was evaluated as Δ (good), and when any one of them had ×, it was evaluated as × (poor).
＜実炉評価＞
炉壁温度が１２００℃の焼成炉の炉壁として２ケ月使用後、１０カ所ランダムに測定した平均値において、元の施工厚に対して残存厚みが９０％以上の場合を〇（合格）、９０％未満の場合を×（不合格）とした。
<Actual furnace evaluation>
After using it as a furnace wall for a baking furnace with a furnace wall temperature of 1200 ° C for 2 months, if the remaining thickness is 90% or more of the original construction thickness in the average value measured randomly at 10 locations, it is 〇 (pass), 90. If it was less than%, it was marked as x (failed).
表１中、実施例１～１２は本発明の範囲内にある乾式吹付材である。これらの総合評価は〇（優良）又は△（良好）であり、耐摩耗性、耐食性、耐スポーリング性のいずれも良好な評価が得られた。なかでも実施例８～１１は、珪酸アルカリ及びリン酸アルカリの含有量、炭化硼素の含有量、炭化硼素の粒度構成、及び粒径７５μｍ未満の原料由来のＳｉＯ２成分の含有量が上述の好ましい範囲内にある乾式吹付材である。その総合評価は〇（優良）であり、その他の実施例に比べてより良好な評価が得られた。 In Table 1, Examples 1 to 12 are drywall spray materials within the scope of the present invention. These comprehensive evaluations were 〇 (excellent) or Δ (good), and good evaluations were obtained in all of wear resistance, corrosion resistance, and spalling resistance. Among them, in Examples 8 to 11, the above-mentioned preferable contents are the content of alkali silicate and alkali phosphate, the content of boron carbide, the particle size composition of boron carbide, and the content of SiO 2 component derived from a raw material having a particle size of less than 75 μm. It is a dry spray material within the range. The overall evaluation was 〇 (excellent), and a better evaluation was obtained as compared with the other examples.
比較例１は、炭化硼素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。
一方、比較例２は、炭化硼素の含有量が多い例であり、耐食性及び耐スポーリング性の評価が×（不良）となった。
Comparative Example 1 is an example in which the content of boron carbide is small, and the evaluation of wear resistance is × (defective).
On the other hand, Comparative Example 2 was an example in which the content of boron carbide was high, and the evaluation of corrosion resistance and spalling resistance was x (poor).
比較例３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、耐摩耗性及び耐食性の評価が×（不良）となった。 Comparative Example 3 is an example in which the content of the SiO 2 component derived from a raw material having a particle size of less than 75 μm is small, and the evaluation of wear resistance and corrosion resistance is × (defective).
比較例４は、珪酸アルカリ及びリン酸アルカリを含有しない例であり、耐摩耗性の評価が×（不良）となった。
一方、比較例５は、珪酸アルカリの含有量が多い例であり、耐食性の評価が×（不良）となった。
Comparative Example 4 is an example in which the alkali silicate and the alkali phosphate are not contained, and the evaluation of wear resistance is × (defective).
On the other hand, Comparative Example 5 is an example in which the content of alkali silicate is high, and the evaluation of corrosion resistance is × (poor).
比較例６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、耐食性の評価が×（不良）となった。 Comparative Example 6 is an example in which the firing temperature assuming the furnace wall temperature of the firing furnace is high, and the evaluation of corrosion resistance is × (defective).
Claims (3)
粉末状の珪酸アルカリ及びリン酸アルカリのうちの１種又は２種以上を合計で０．２質量％以上１０質量％以下、炭化硼素を０．３質量％以上５質量％以下、残部に主として、アルミナ原料、シリカ原料、アルミナ－シリカ質原料、炭化珪素原料、マグネシア原料、マグネシア－カルシア質原料、及びこれらの原料の少なくとも１種を含む使用後耐火物原料から選択される１種又は２種以上を含有し、
当該乾式吹付材の総量１００質量％中に、粒径７５μｍ未満の原料由来のＳｉＯ２成分を７質量％以上含有する、焼成炉用の乾式吹付材。 A drywall spray material for firing furnaces with a furnace wall temperature of 1400 ° C or less.
A total of 0.2% by mass or more and 10% by mass or less of one or two or more of powdered alkali silicate and alkali phosphate, 0.3% by mass or more and 5% by mass or less of boron carbide, mainly in the balance. One or more selected from post-use refractory raw materials including alumina raw materials, silica raw materials, alumina-silicic raw materials, silicon carbide raw materials, magnesia raw materials, magnesia-calcia raw materials, and at least one of these raw materials. Contains,
A dry-type spray material for a firing furnace, which contains 7% by mass or more of a SiO 2 component derived from a raw material having a particle size of less than 75 μm in a total amount of 100% by mass of the dry-type spray material.
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