JP2008088044A - Monolithic refractory and waste melting furnace - Google Patents
Monolithic refractory and waste melting furnace Download PDFInfo
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- 238000002844 melting Methods 0.000 title claims abstract description 46
- 230000008018 melting Effects 0.000 title claims abstract description 46
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 239000011823 monolithic refractory Substances 0.000 title abstract 4
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- 239000006104 solid solution Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 27
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 19
- 239000011651 chromium Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 15
- 239000011819 refractory material Substances 0.000 claims description 10
- 238000010276 construction Methods 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 230000003628 erosive effect Effects 0.000 abstract description 25
- 229910020068 MgAl Inorganic materials 0.000 abstract description 10
- 239000000243 solution Substances 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 45
- 239000000395 magnesium oxide Substances 0.000 description 27
- 239000011777 magnesium Substances 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 239000002270 dispersing agent Substances 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 11
- 229910000480 nickel oxide Inorganic materials 0.000 description 11
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000002893 slag Substances 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
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- 229920000570 polyether Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
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- 235000010339 sodium tetraborate Nutrition 0.000 description 1
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- VXYADVIJALMOEQ-UHFFFAOYSA-K tris(lactato)aluminium Chemical compound CC(O)C(=O)O[Al](OC(=O)C(C)O)OC(=O)C(C)O VXYADVIJALMOEQ-UHFFFAOYSA-K 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- Ceramic Products (AREA)
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Abstract
Description
本発明は、廃棄物溶融炉に適したクロムフリー不定形耐火物及びこのクロムフリー不定形耐火物を使用した廃棄物溶融炉に関するものである。 The present invention relates to a chromium-free amorphous refractory suitable for a waste melting furnace and a waste melting furnace using the chromium-free amorphous refractory.
近年、都市ゴミや廃棄物の発生量が急増しており、その処理は大きな社会問題となっている。この対策として、溶融法すなわち廃棄物の減容化、無害化または再資源化が注目されている。溶融法は廃棄物中の無機物を溶融スラグとして取り出し、大幅に減容する方法である。 In recent years, the amount of municipal waste and waste generated has increased rapidly, and its disposal has become a major social problem. As a countermeasure, a melting method, that is, a volume reduction, detoxification, or recycling of waste is attracting attention. The melting method is a method of taking out inorganic substances in waste as molten slag and greatly reducing the volume.
溶融炉に使用される耐火物の侵食スピードは、投入される焼却灰、飛灰、下水汚泥等の組成及び溶融温度に大きく左右される。溶融スラグの組成は廃棄物の種類によって大きく変動するが、一般的には、SiO2:15〜45重量%、Al2O3:10〜20重量%、CaO:5〜45重量%、Na2O1〜15重量%、K2O1〜15重量%であり、塩基度(C/S)で0.5〜2.0程度と処理物により大きく変動する。この他、焼却灰や飛灰には、Cd、Pb、Zn、Cu、As、Cr、Hg等の有害な金属も多く含まれている。さらに揮発成分としてSやClも多く含まれ、溶融温度を1200〜1650℃の高温にする必要がある。また、温度変化の激しい溶融炉では熱衝撃による損傷もある。The erosion speed of the refractory used in the melting furnace greatly depends on the composition and melting temperature of incinerated ash, fly ash, sewage sludge and the like. Although the composition of the molten slag varies greatly depending on the type of waste, in general, SiO 2: 15 to 45 wt%, Al 2 O 3: 10~20 wt%, CaO: 5 to 45 wt%, Na 2 O1~15 wt%, a K 2 O1~15 wt%, varies greatly by treatment equivalent to about 0.5 to 2.0 in basicity (C / S). In addition, incinerated ash and fly ash contain many harmful metals such as Cd, Pb, Zn, Cu, As, Cr, and Hg. Further, a large amount of S and Cl are contained as volatile components, and the melting temperature must be set to a high temperature of 1200 to 1650 ° C. Further, in a melting furnace where the temperature changes drastically, there is damage due to thermal shock.
したがって現在は、耐食性の点からCr2O3を含む耐火物としてAl2O3とCr2O3からなる耐火物が使用されている。Cr2O3含有耐火物はC2O3含有量が多いほど耐食性がよい(特許文献1参照)。しかし、Cr2O3含有量が多くなると、耐熱衝撃性の低下や、耐火物中のCr2O3が高温かつアルカリ共存雰囲気下で使用されると有害な六価クロムに変化するため、環境汚染問題を生じるおそれがある。またCr2O3含有量が多いほど六価クロムの生成量も多い。Therefore currently, refractories consisting of Al 2 O 3 and Cr 2 O 3 as a refractory material containing Cr 2 O 3 from corrosion resistance point is used. The higher the C 2 O 3 content, the better the corrosion resistance of the Cr 2 O 3 -containing refractory (see Patent Document 1). However, when the Cr 2 O 3 content is increased, the thermal shock resistance is reduced, and when Cr 2 O 3 in the refractory is used in a high-temperature and alkali-existing atmosphere, it changes to harmful hexavalent chromium. May cause contamination problems. Further, the higher the Cr 2 O 3 content, the greater the amount of hexavalent chromium produced.
また、Cr2O3を含有しない耐火物として、Al2O3−ZrO2質(特許文献2参照)、Al2O3−MgO質(特許文献3参照)、Al2O3−SiC(特許文献4参照)、Al2O3−NiO(特許文献5参照)が知られているが、いずれも使用条件の厳しい溶融炉用耐火物として十分な耐用を示していない。
従来のクロムフリー不定形耐火物は廃棄物溶融炉での使用において、その耐用は酸化クロム含有品に比べて大きく劣る。廃棄物溶融炉のスラグはアルカリ成分が多い為、Al2O3−ZrO2質、あるいはAl2O3−MgO質はZrO2、MgO成分がスラグ中に溶出し、耐溶損性に劣る。また、Al2O3−SiC質は廃棄物溶融炉の酸化雰囲気では炭化珪素が酸化され、耐溶損性に劣る。Al2O3−NiO質ではCr2O310%程度の耐溶損性しか得ることができない。Conventional chrome-free amorphous refractories are greatly inferior to chromium-containing products when used in a waste melting furnace. Since the slag of the waste melting furnace has many alkali components, Al 2 O 3 —ZrO 2 or Al 2 O 3 —MgO is eluted with ZrO 2 and MgO components in the slag, and is inferior in resistance to erosion. In addition, Al 2 O 3 —SiC is inferior in resistance to erosion because silicon carbide is oxidized in an oxidizing atmosphere of a waste melting furnace. In the case of Al 2 O 3 —NiO, it is possible to obtain only melt resistance of about 10% of Cr 2 O 3 .
本発明は廃棄物溶融炉の内張りとして、Cr2O3含有品相当の優れた耐溶損性を有すクロムフリー不定形耐火物とこれを内張りに使用した廃棄物溶融炉を提供するものである。The present invention provides, as a lining of a waste melting furnace, a chromium-free amorphous refractory having an excellent erosion resistance equivalent to a Cr 2 O 3 containing product and a waste melting furnace using the same for the lining. .
(1)Al2O3質原料を含む耐火性原料組成に結合剤及び分散剤を添加してなる不定形耐火物に、(Mg,Ni)Oの固溶体を1〜85重量%添加することにより、耐溶損性に優れたクロムフリー不定形耐火物を得た。これは廃棄物溶融炉用クロムフリー不定形耐火物として有用である。また、TiO2やZrO2等の他耐火性成分が含まれても同様の効果を示す。(1) By adding 1 to 85% by weight of a solid solution of (Mg, Ni) O to an amorphous refractory formed by adding a binder and a dispersant to a refractory raw material composition containing an Al 2 O 3 raw material As a result, a chromium-free amorphous refractory having excellent melt resistance was obtained. This is useful as a chromium-free amorphous refractory for waste melting furnaces. Moreover, even if other refractory components such as TiO 2 and ZrO 2 are included, the same effect is exhibited.
(2)MgAl2O4質原料を含む耐火性原料組成に結合剤及び分散剤を添加してなる不定形耐火物に、(Mg,Ni)Oの固溶体を1〜85重量%添加することにより、耐溶損性に優れたクロムフリー不定形耐火物を得た。これは廃棄物溶融炉用クロムフリー不定形耐火物として有用である。また、TiO2やZrO2等の他耐火性成分が含まれても同様の効果を示す。(2) By adding 1 to 85% by weight of a solid solution of (Mg, Ni) O to an amorphous refractory obtained by adding a binder and a dispersant to a refractory raw material composition containing MgAl 2 O 4 material As a result, a chromium-free amorphous refractory having excellent melt resistance was obtained. This is useful as a chromium-free amorphous refractory for waste melting furnaces. Moreover, even if other refractory components such as TiO 2 and ZrO 2 are included, the same effect is exhibited.
(3)Al2O3質原料を含む耐火性原料組成に結合剤及び分散剤を添加してなる不定形耐火物で全組成中にMgOとNiOの2成分を含み、その化学成分の合計量を5〜85重量%とすることにより、耐溶損性に優れたクロムフリー不定形耐火物を得た。これは廃棄物溶融炉用クロムフリー不定形耐火物として有用である。また、TiO2やZr2等の他耐火性成分が含まれても同様の効果を示す。(3) An amorphous refractory material obtained by adding a binder and a dispersant to a refractory raw material composition containing an Al 2 O 3 raw material, including the two components MgO and NiO in the total composition, and the total amount of the chemical components By making the content of 5 to 85% by weight, a chromium-free amorphous refractory having excellent melt resistance was obtained. This is useful as a chromium-free amorphous refractory for waste melting furnaces. Moreover, even if other refractory components such as TiO 2 and Zr 2 are included, the same effect is exhibited.
(4)MgAl2O4質原料を含む耐火性原料組成に結合剤及び分散剤を添加してなる不定形耐火物で全組成中にMgOとNiOの2成分を含み、その化学成分の合計量を5〜85重量%とすることにより、耐溶損性に優れたクロムフリー不定形耐火物を得た。これは廃棄物溶融炉用クロムフリー不定形耐火物として有用である。また、TiO2やZrO2等の他耐火性成分が含まれても同様の効果を示す。(4) An amorphous refractory material obtained by adding a binder and a dispersant to a refractory raw material composition containing MgAl 2 O 4 raw material, including two components of MgO and NiO in the total composition, and the total amount of the chemical components By making the content of 5 to 85% by weight, a chromium-free amorphous refractory having excellent melt resistance was obtained. This is useful as a chromium-free amorphous refractory for waste melting furnaces. Moreover, even if other refractory components such as TiO 2 and ZrO 2 are included, the same effect is exhibited.
前記(1)項ないし(4)項記載のいずれか1項に記載の廃棄物溶融炉用クロムフリー不定形耐火物を流し込み施工またはプレキャスト施工にて炉の少なくとも一部に使用した廃棄物溶融炉。 Waste melting furnace used for at least a part of the furnace by casting or precasting the chromium-free amorphous refractory for waste melting furnace according to any one of items (1) to (4) .
本発明の耐火物はCr2O3成分を含まないクロムフリー不定形耐火物であり、廃棄物溶融炉特有の高アルカリスラグと高温操業という過酷な使用条件下で十分な耐溶損性を発揮する。その結果、本発明のクロムフリー不定形耐火物は耐火物寿命の延長による溶融炉稼働率及び耐火物原単位を向上させると共に、使用後に発生する六価クロムによる環境汚染問題を解決する。The refractory of the present invention is a chromium-free amorphous refractory that does not contain Cr 2 O 3 component, and exhibits sufficient resistance to erosion under severe use conditions such as high alkali slag and high temperature operation unique to waste melting furnaces. . As a result, the chromium-free amorphous refractory of the present invention improves the operating rate of the melting furnace and the refractory unit by extending the life of the refractory, and solves the environmental pollution problem caused by hexavalent chromium generated after use.
Al2O3質原料を含む耐火性原料組成に結合剤及び分散剤を添加してなる不定形耐火物に(Mg,Ni)Oの固溶体を1〜85重量%添加することにより、Cr2O3含有品相当の優れた耐食性を得ることができる。By adding 1 to 85% by weight of a solid solution of (Mg, Ni) O to an amorphous refractory obtained by adding a binder and a dispersant to a refractory raw material composition containing an Al 2 O 3 raw material, Cr 2 O Excellent corrosion resistance equivalent to 3 containing products can be obtained.
MgAl2O4質原料を含む耐火性原料組成に結合剤及び分散剤を添加してなる不定形耐火物に(Mg,Ni)Oの固溶体を1〜85重量%添加することにより、Cr2O3含有品相当の優れた耐食性を得ることができる。By adding 1 to 85% by weight of a solid solution of (Mg, Ni) O to an amorphous refractory obtained by adding a binder and a dispersant to a refractory raw material composition containing a MgAl 2 O 4 material, Cr 2 O Excellent corrosion resistance equivalent to 3 containing products can be obtained.
Al2O3質原料を含む耐火性原料組成に結合剤及び分散剤を添加してなる不定形耐火物で全組成中にMgOとNiOの2成分を含み、その化学成分の合計量を5〜85重量%とすることにより、廃棄物溶融炉にて使用中に(Mg,Ni)Oの固溶体を生成することによって、Cr2O3含有品相当の優れた耐食性を得ることができる。An amorphous refractory formed by adding a binder and a dispersant to a refractory raw material composition containing an Al 2 O 3 raw material, including two components of MgO and NiO in the entire composition, and the total amount of the chemical components is 5 to By setting it to 85% by weight, excellent corrosion resistance equivalent to a Cr 2 O 3 -containing product can be obtained by generating a solid solution of (Mg, Ni) O during use in a waste melting furnace.
MgAl2O4質原料を含む耐火性原料組成に結合剤及び分散剤を添加してなる不定形耐火物で全組成中にMgOとNiOの2成分を含み、その化学成分の合計量を5〜85重量%とすることにより、廃棄物溶融炉にて使用中に(Mg,Ni)Oの固溶体を生成することによって、Cr2O3含有品相当の優れた耐食性を得ることができる。An amorphous refractory material obtained by adding a binder and a dispersant to a refractory raw material composition containing MgAl 2 O 4 -based raw material, including two components of MgO and NiO in the entire composition, and the total amount of the chemical components is 5 to By setting it to 85% by weight, excellent corrosion resistance equivalent to a Cr 2 O 3 -containing product can be obtained by generating a solid solution of (Mg, Ni) O during use in a waste melting furnace.
本発明における(Mg,Ni)0固溶体中のNiOは10重量%以上が望ましい。NiO成分が10重量%未満になると優れた耐溶損性は期待できない。 The NiO in the (Mg, Ni) 0 solid solution in the present invention is preferably 10% by weight or more. When the NiO component is less than 10% by weight, excellent melt resistance cannot be expected.
本発明において、使用する(Mg,Ni)Oの固溶体として、MgOとNiOを焼成して得られる焼結(Mg,Ni)O固溶体と、MgOとNiOを溶融して得られる溶融(Mg,Ni)O固溶体がある。溶融(Mg,Ni)O固溶体を使用した場合、最も大きな効果が得られる。 In the present invention, as a solid solution of (Mg, Ni) O to be used, a sintered (Mg, Ni) O solid solution obtained by firing MgO and NiO, and a melt (Mg, Ni) obtained by melting MgO and NiO ) There is O solid solution. When a molten (Mg, Ni) O solid solution is used, the greatest effect is obtained.
本発明において、使用する(Mg,Ni)Oの固溶体は気孔率が5%以下のものが好ましい。 In the present invention, the solid solution of (Mg, Ni) O used preferably has a porosity of 5% or less.
本発明におけるNiO原料のNiO成分純度は99重量%以上が好ましい。 The NiO component purity of the NiO raw material in the present invention is preferably 99% by weight or more.
本発明におけるMgO原料のMgO成分純度は99重量%以上が好ましい。 The MgO component purity of the MgO raw material in the present invention is preferably 99% by weight or more.
NiO含有原料の粒度は平均粒径45μm以下の微粒子としての使用が好ましい。 The NiO-containing raw material is preferably used as fine particles having an average particle size of 45 μm or less.
本発明において、使用するMgAl2O4質原料は理論組成であるMgO成分28%、Al2O3成分72%に近いものが最も望ましいが、MgO成分とAl2O3成分の成分比を変えたスピネル粒子を使用しても効果はある。In the present invention, MgO ingredient 28% MgAl 2 O 4 feedstocks used are theoretical composition, but close to Al 2 O 3 component 72% is most desirable, the component ratio of the MgO component and Al 2 O 3 component changed Use of spinel particles is also effective.
本発明において、使用するMgAl2O4質原料として、Al2O3とMgOを焼成して得られる焼結MgAl2O4質原料と、Al2O3とMgOを溶融して得られる溶融MgAl2O4質原料がある。溶融MgAl2O4質原料を使用した場合、最も大きな効果が得られる。In the present invention, as MgAl 2 O 4 feedstocks used, Al 2 O 3 and sintering MgAl 2 O 4 feedstocks obtained MgO was calcined, molten MgAl obtained by melting Al 2 O 3 and MgO There are 2 O 4 quality raw materials. When a molten MgAl 2 O 4 material is used, the greatest effect is obtained.
本発明における(Mg,Ni)O固溶体の添加量は50重量%程度で最も優れた耐溶損性を得ることができる。70重量%まで添加しても、50重量%添加品とでは、耐溶損性に変わりはない。70重量%を越えると70重量%添加品より耐溶損性は劣る結果となる。 In the present invention, the addition amount of the (Mg, Ni) O solid solution is about 50% by weight, and the most excellent resistance to erosion can be obtained. Even if it is added up to 70% by weight, it does not change the resistance to melting with the 50% by weight added product. When it exceeds 70% by weight, the resistance to melting loss is inferior to that of the 70% by weight added product.
本発明における不定形耐火物で全組成中にMgOとNiOの2成分を含み、その化学成分の合計量が50重量%程度で最も優れた耐溶損性を得ることができる。化学成分の合計量が70重量%までが優れた耐溶損性を得ることができる。化学成分の合計量が70重量%添加品と50重量%添加品とでは、耐溶損性に変わりはない。化学成分の合計量が70重量%を越えるとそのものより耐溶損性は劣る結果となる。 The amorphous refractory according to the present invention contains two components of MgO and NiO in the entire composition, and the most excellent resistance to erosion can be obtained when the total amount of the chemical components is about 50% by weight. Excellent resistance to erosion can be obtained when the total amount of chemical components is up to 70% by weight. In the case where the total amount of chemical components is 70% by weight and 50% by weight, there is no change in the resistance to melting. When the total amount of the chemical components exceeds 70% by weight, the melt resistance is inferior to that of itself.
本発明の効果を阻害しない範囲であれば耐火性原料として、さらにシリカ、ムライト、ドロマイト、カルシア、ジルコン、ジルコニア、チタニア、炭化珪素、炭素、イットリア等から選ばれる一種または二種以上使用してもよい。 As long as it does not inhibit the effect of the present invention, it may be used as a refractory raw material, further one or more selected from silica, mullite, dolomite, calcia, zircon, zirconia, titania, silicon carbide, carbon, yttria, etc. Good.
本発明の不定形耐火物は環境汚染防止のために、実質的にCr2O3を含まない。ここで実質的に含まないとは、Cr2O3を含んでいても例えば0.1重量%以下の不純物あるいはMgO質原料の消化防止剤的な量とする。The amorphous refractory according to the present invention does not substantially contain Cr 2 O 3 in order to prevent environmental pollution. Here, the term “substantially free” means, for example, 0.1% by weight or less of impurities or MgO-based raw material as an anti-digestive amount even if Cr 2 O 3 is contained.
不定形耐火物の施工性のための技術常識として、結合剤及び分散剤が添加されろが、これらの材質、添加量は従来と特に変わりない。結合剤は、例えばアルミナセメント、マグネシアセメント、ポルトランドセメント、水硬性アルミナ、オキシカルボン酸アルミニウム、リン酸塩、ケイ酸塩、シリカゾル、フェノール樹脂等から選ばれる一種または二種以上使用してもよい。中でも施工体強度及び耐熱性を付与したアルミナセメントが好ましい。結合剤の添加は耐火原料組成100重量%に対する外掛けで、1〜15重量%が好ましい。 As a technical common sense for the workability of the amorphous refractory, a binder and a dispersant are added. However, these materials and addition amounts are not particularly different from conventional ones. The binder may be used alone or in combination of two or more selected from alumina cement, magnesia cement, Portland cement, hydraulic alumina, aluminum oxycarboxylate, phosphate, silicate, silica sol, phenol resin, and the like. Among these, alumina cement imparted with construction body strength and heat resistance is preferable. The addition of the binder is an outer coating with respect to 100% by weight of the refractory raw material composition, and preferably 1 to 15% by weight.
分散剤は不定形耐火物施工時の流動性を付与する効果を持つ。分散剤の材質は従来から様々のものが提案されている。本発明における分散剤の種類は限定されるものではないが、トリポリリン酸ソーダ、ヘキサメタリン酸ソーダ、酸性ヘキサメタリン酸ソーダ、ウルトラポリリン酸ソーダ、クエン酸ソーダ、ホウ酸ソーダ、酒石酸ソーダ、カルボキシル基含有ポリエーテル、ポリアクリル酸ソーダ、ポリカルボン酸ソーダ、スルホン酸ソーダ、リグニンスルホン酸ソーダ等である。 The dispersant has the effect of imparting fluidity during construction of the irregular refractory. Various materials for the dispersant have been proposed. The type of the dispersant in the present invention is not limited, but includes sodium tripolyphosphate, sodium hexametaphosphate, acidic hexametaphosphate soda, ultrapolyphosphate soda, sodium citrate, sodium borate, sodium tartrate, carboxyl group-containing polyether Polyacrylic acid soda, polycarboxylic acid soda, sulfonic acid soda, lignin sulfonic acid soda, and the like.
分散剤の添加量は、耐火原料100重量%に対する外掛けで0.01〜1重量%が好ましい。 The addition amount of the dispersant is preferably 0.01 to 1% by weight as an outer coating with respect to 100% by weight of the refractory raw material.
本発明の不定形耐火物は以上の他にも必要によっては硬化調整剤、乳酸アルミニウム、有機繊維、金属、ガラス等を添加してもよい。これらの添加量は耐火原料組成100重量%に対する外掛けで5重量%以下が望ましい。 In addition to the above, the amorphous refractory of the present invention may contain a curing regulator, aluminum lactate, organic fiber, metal, glass and the like as necessary. These addition amounts are desirably 5% by weight or less as an outer coating with respect to 100% by weight of the refractory raw material composition.
施工には以上の配合組成物全体に対する外掛けで、水分2〜8重量%程度添加して混練して、型枠を用いて流し込み施工する。流し込みの際には振動を付与して充填を図る。施工後は養生・乾燥を行なう。この施工は炉に直接流し込み施工する他、別場所で型枠に流し込み施工して得たプレモールド品を用いたプレモールド法をもって内張りしても良い。 In the construction, about 2 to 8% by weight of water is added and kneaded with the outer coating for the entire blended composition described above, and cast using a mold. When pouring, filling is performed by applying vibration. Curing and drying after construction. This construction may be performed by pouring directly into the furnace, or may be lined by a pre-mold method using a pre-molded product obtained by pouring into a mold at another location.
表1と表2に使用した原料の化学成分を示した。 Tables 1 and 2 show the chemical components of the raw materials used.
表3から表7までに本発明の比較例を示し、さらに各例の試験結果を示す。 Tables 3 to 7 show comparative examples of the present invention, and further show the test results of each example.
表8から表16までに本発明の実施例を示し、さらに各例の試験結果を示す。 Tables 8 to 16 show examples of the present invention, and further show test results of the examples.
耐食性の評価方法は次のとおりである。 The evaluation method of corrosion resistance is as follows.
回転侵食ドラム法にて1500℃×24時間の侵食試験を塩基度1.0のスラグの条件で行い、双方の原寸より侵食量の合計数値(mm)を示した。 An erosion test at 1500 ° C. for 24 hours was performed by the rotary erosion drum method under the condition of a slag having a basicity of 1.0, and the total value (mm) of the erosion amount was shown from both original dimensions.
比較例1から比較例4は、酸化クロム含有品である比較例5と比較して耐溶損性が大きく劣る。 Comparative Example 1 to Comparative Example 4 are greatly inferior in resistance to melting as compared with Comparative Example 5 which is a chromium oxide-containing product.
比較例1に(Mg,Ni)O固溶体を添加した比較例6から9は大きな耐溶損性の向上は認められない。 In Comparative Examples 6 to 9 in which the (Mg, Ni) O solid solution is added to Comparative Example 1, no significant improvement in resistance to melting loss is observed.
比較例7に理論スピネルを1重量%添加した比較例10でも大きな耐溶損性の向上は認められない。 Even in Comparative Example 10 in which 1% by weight of theoretical spinel is added to Comparative Example 7, no significant improvement in the erosion resistance is observed.
実施例26から実施例30は(Mg,Ni)O固溶体の添加量を70重量%以上の添加品となるが、実施例にある(Mg,Ni)O固溶体の添加量を70重量%品の実施例5,実施例10,実施例20よりも耐溶損性は劣る結果となった。 In Examples 26 to 30, the added amount of the (Mg, Ni) O solid solution is 70% by weight or more, but the added amount of the (Mg, Ni) O solid solution in the example is 70% by weight. As a result, the melt resistance was inferior to that of Example 5, Example 10, and Example 20.
比較例11から比較例15は耐火物内に酸化マグネシウムと酸化ニッケルを含みその化学組成の合計量が5重量%以下のものであるが、比較例1と比較しても大きな耐溶損性の向上は認められない。 Comparative Example 11 to Comparative Example 15 contain magnesium oxide and nickel oxide in the refractory, and the total amount of the chemical composition is 5% by weight or less. It is not allowed.
実施例46から実施例50は耐火物内に酸化マグネシウムと酸化ニッケルを含みその化学組成の合計量が70重量%以上のものであるが、実施例にある耐火物内に酸化マグネシウムと酸化ニッケルを含みその化学組成の合計量が70重量%付近の実施例45,実施例55よりも耐溶損性は劣る結果となった。 Examples 46 to 50 include magnesium oxide and nickel oxide in the refractory and the total amount of the chemical composition is 70% by weight or more. Magnesium oxide and nickel oxide are contained in the refractory in the example. In addition, the corrosion resistance was inferior to those of Examples 45 and 55 in which the total amount of the chemical composition was about 70% by weight.
実施例1から実施例5は比較例1に(Mg,Ni)O−5を添加したものである。添加量が増えるに従い耐溶損性は向上する。添加量が50重量%付近で耐溶損性は最も優れ、添加量が70重量%までほぼ平行線である。 In Examples 1 to 5, (Mg, Ni) O-5 was added to Comparative Example 1. As the amount of addition increases, the resistance to erosion improves. When the addition amount is around 50% by weight, the corrosion resistance is the best, and the addition amount is almost parallel up to 70% by weight.
実施例6から実施例10は比較例1に(Mg,Ni)O−10cを添加したものである。添加量が増えるに従い耐溶損性は向上する。添加量が50重量%付近で耐溶損性は最も優れ、添加量が70重量%までほぼ平行線である。 Examples 6 to 10 are obtained by adding (Mg, Ni) O-10c to Comparative Example 1. As the amount of addition increases, the resistance to erosion improves. When the addition amount is around 50% by weight, the corrosion resistance is the best, and the addition amount is almost parallel up to 70% by weight.
実施例11から実施例15は実施例6から10の(Mg,Ni)O−10cを溶融品である(Mg,Ni)O−10bに変更したものである。同じ組成の(Mg,Ni)O固溶体でも溶融品の使用が最も優れた耐溶損性を示した。また、添加量が増えるに従い耐溶損性は向上する。添加量が50重量%付近で耐溶損性は最も優れ、添加量が70重量%までほぼ平行線である。 In Examples 11 to 15, (Mg, Ni) O-10c of Examples 6 to 10 is changed to (Mg, Ni) O-10b which is a molten product. Even when the (Mg, Ni) O solid solution having the same composition was used, the use of a molten product showed the most excellent resistance to erosion. In addition, as the amount added increases, the resistance to erosion improves. When the addition amount is around 50% by weight, the corrosion resistance is the best, and the addition amount is almost parallel up to 70% by weight.
実施例16から実施例20は比較例1に(Mg,Ni)O−20を添加したものである。添加量が増えるに従い耐溶損性は向上する。添加量が50重量%付近で耐溶損性は最も優れ、添加量が70重量%までほぼ平行線である。 Examples 16 to 20 are obtained by adding (Mg, Ni) O-20 to Comparative Example 1. As the amount of addition increases, the resistance to erosion improves. When the addition amount is around 50% by weight, the corrosion resistance is the best, and the addition amount is almost parallel up to 70% by weight.
実施例21から実施例25は比較例1にMgO−NiO−TiO2を添加したものである。添加量が増えるに従い耐溶損性は向上する。添加量が50重量%付近で耐溶損性は最も優れ、添加量が70重量%までほぼ平行線である。実施例6から実施例10との違いは他耐火性成分としてTiO2を含んでいることである。TiO2を含むことによる耐溶損性の低下は認められない。In Examples 21 to 25, MgO—NiO—TiO 2 was added to Comparative Example 1. As the amount of addition increases, the resistance to erosion improves. When the addition amount is around 50% by weight, the corrosion resistance is the best, and the addition amount is almost parallel up to 70% by weight. The difference from Example 6 to Example 10 is that TiO 2 is included as another refractory component. The deterioration of the melt resistance due to the inclusion of TiO 2 is not recognized.
実施例7と実施例31では、添加している(Mg,Ni)O−10の気孔率が実施例7では3%であるのに対し、実施例31では気孔率が15%である。この差により実施例7の方が優れた耐溶損性を示した。このことより、添加する(Mg,Ni)O固溶体の気孔率は小さいほど好ましいことが解る。 In Example 7 and Example 31, the porosity of the added (Mg, Ni) O-10 is 3% in Example 7, whereas in Example 31, the porosity is 15%. Due to this difference, Example 7 showed better melt resistance. From this, it can be seen that the smaller the porosity of the (Mg, Ni) O solid solution added, the better.
実施例32から実施例35は実施例7に理論スピネルを添加したものである。理論スピネルの添加量が増えるに従い耐溶損性は向上する。 Examples 32 to 35 are obtained by adding theoretical spinel to Example 7. As the amount of theoretical spinel added increases, the erosion resistance improves.
実施例36と実施例37では、添加している酸化ニッケルの平均粒径が実施例36では45μm以下に対し、実施例37では45μmより大きい。この差により実施例36の方が優れた耐溶損性を示した。このことより、添加する酸化ニッケルの平均粒径は小さいほど好ましいことが解る。 In Example 36 and Example 37, the average particle diameter of the added nickel oxide is 45 μm or less in Example 36, whereas it is larger than 45 μm in Example 37. Due to this difference, Example 36 showed superior resistance to melting damage. From this, it is understood that the smaller the average particle diameter of the nickel oxide to be added, the better.
実施例41から実施例45は比較例1に酸化マグネシウムと酸化ニッケルの2成分の合計量を5重量%以上添加したものである。添加量が増えるに従い耐溶損性は向上する。添加量合計が50重量%付近で耐溶損性は最も優れ、添加量合計が70重量%までほぼ平行線である。 In Examples 41 to 45, the total amount of two components of magnesium oxide and nickel oxide is added to Comparative Example 1 in an amount of 5% by weight or more. As the amount of addition increases, the resistance to erosion improves. When the total addition amount is around 50% by weight, the resistance to erosion is most excellent, and the total addition amount is almost parallel to 70% by weight.
実施例43と実施例51では、添加している酸化ニッケルの平均粒径が実施例43では45μm以下に対し、実施例51では45μmより大きい。この差により実施例43の方が優れた耐溶損性を示した。このことより、添加する酸化ニッケルの平均粒径は小さいほど好ましいことが解る。 In Example 43 and Example 51, the average particle diameter of the added nickel oxide is 45 μm or less in Example 43, whereas it is larger than 45 μm in Example 51. Due to this difference, Example 43 showed better melt resistance. From this, it is understood that the smaller the average particle diameter of the nickel oxide to be added, the better.
実施例52から実施例54は実施例42から実施例44の溶融アルミナを理論スピネルに変更したものである。この結果より、溶融アルミナを理論スピネルに変更することが、さらなる耐溶損性の向上に繋がることがわかる。 In Examples 52 to 54, the molten alumina of Examples 42 to 44 is changed to a theoretical spinel. From this result, it can be seen that changing molten alumina to theoretical spinel leads to further improvement in resistance to melting.
いずれもMgOとNiO添加品は優れた結果を示した。中でもMgO+NiO量が35重量%以上になると酸化クロム20重量%品と同等ないしはそれ以上の耐スラグ溶損性を示した。 In both cases, MgO and NiO-added products showed excellent results. Above all, when the amount of MgO + NiO was 35% by weight or more, the slag erosion resistance was equal to or more than that of 20% by weight of chromium oxide.
実施例9に示した組成の不定形耐火物を飛灰溶融炉の湯口で使用したところ、比較例5で170日耐用のところ、180日以上の高耐用が得られた。 When the amorphous refractory having the composition shown in Example 9 was used at the gate of the fly ash melting furnace, 170 days in Comparative Example 5 yielded high durability of 180 days or more.
酸化マグネシウムと酸化ニッケルを併用したクロムフリー不定形耐火物は酸化マグネシウムと酸化ニッケル固溶体を作ることにより優れた耐スラグ溶損性を示した。また、すでには酸化マグネシウムと酸化ニッケル固溶体として作成した原料を添加しても同様の優れた耐スラグ溶損性を示す。このことにより、酸化クロム含有耐火物の使用を制限し、六価クロムの問題を軽減することができる。 Chromium-free amorphous refractories combined with magnesium oxide and nickel oxide showed excellent slag erosion resistance by making magnesium oxide and nickel oxide solid solution. Moreover, even if the raw materials already prepared as magnesium oxide and nickel oxide solid solution are added, the same excellent slag erosion resistance is exhibited. This limits the use of chromium oxide-containing refractories and can alleviate the problem of hexavalent chromium.
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JPH08208309A (en) * | 1995-01-27 | 1996-08-13 | Tokyo Yogyo Co Ltd | Basic brick |
JPH08208315A (en) * | 1995-01-27 | 1996-08-13 | Tokyo Yogyo Co Ltd | Basic brick |
JP2001182921A (en) * | 1999-12-27 | 2001-07-06 | Kurosaki Harima Corp | A castable refractory for constructing waste fusing furnace with casting process and waste fusing furnace using the same |
JP2004307277A (en) * | 2003-04-08 | 2004-11-04 | Mino Ceramic Co Ltd | Castable molded article and method of manufacturing the same |
JP2005213120A (en) * | 2004-01-30 | 2005-08-11 | Kurosaki Harima Corp | Monolithic refractory for waste melting furnace and waste melting furnace using the same for lining |
-
2006
- 2006-10-03 JP JP2006298276A patent/JP4967605B2/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08208309A (en) * | 1995-01-27 | 1996-08-13 | Tokyo Yogyo Co Ltd | Basic brick |
JPH08208315A (en) * | 1995-01-27 | 1996-08-13 | Tokyo Yogyo Co Ltd | Basic brick |
JP2001182921A (en) * | 1999-12-27 | 2001-07-06 | Kurosaki Harima Corp | A castable refractory for constructing waste fusing furnace with casting process and waste fusing furnace using the same |
JP2004307277A (en) * | 2003-04-08 | 2004-11-04 | Mino Ceramic Co Ltd | Castable molded article and method of manufacturing the same |
JP2005213120A (en) * | 2004-01-30 | 2005-08-11 | Kurosaki Harima Corp | Monolithic refractory for waste melting furnace and waste melting furnace using the same for lining |
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