JPH0971477A - Electrofused refractory material and refractory using the same - Google Patents
Electrofused refractory material and refractory using the sameInfo
- Publication number
- JPH0971477A JPH0971477A JP7226745A JP22674595A JPH0971477A JP H0971477 A JPH0971477 A JP H0971477A JP 7226745 A JP7226745 A JP 7226745A JP 22674595 A JP22674595 A JP 22674595A JP H0971477 A JPH0971477 A JP H0971477A
- Authority
- JP
- Japan
- Prior art keywords
- component
- refractory material
- electrofused
- mgo
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011819 refractory material Substances 0.000 title claims abstract description 78
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 28
- 239000011707 mineral Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 18
- 229910052566 spinel group Inorganic materials 0.000 claims description 11
- 239000000470 constituent Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 127
- 239000000395 magnesium oxide Substances 0.000 abstract description 63
- 238000004901 spalling Methods 0.000 abstract description 35
- 230000007797 corrosion Effects 0.000 abstract description 29
- 238000005260 corrosion Methods 0.000 abstract description 29
- 235000010755 mineral Nutrition 0.000 abstract description 25
- 239000011230 binding agent Substances 0.000 abstract description 4
- 239000003607 modifier Substances 0.000 abstract description 2
- 229910018404 Al2 O3 Inorganic materials 0.000 abstract 4
- 229910019830 Cr2 O3 Inorganic materials 0.000 abstract 4
- 229910017344 Fe2 O3 Inorganic materials 0.000 abstract 3
- 235000012245 magnesium oxide Nutrition 0.000 description 58
- 239000011449 brick Substances 0.000 description 35
- 239000000047 product Substances 0.000 description 31
- 239000002994 raw material Substances 0.000 description 27
- 239000011651 chromium Substances 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 229910052596 spinel Inorganic materials 0.000 description 17
- 239000011029 spinel Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 11
- 238000005336 cracking Methods 0.000 description 10
- 239000007858 starting material Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000002893 slag Substances 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011451 fired brick Substances 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000013003 hot bending Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 210000002808 connective tissue Anatomy 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001570 bauxite Inorganic materials 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
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000011452 unfired brick Substances 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、溶融金属保持炉、
精錬炉、真空脱ガス炉等に使用される耐火物用の電融耐
火材料及びこれを用いた耐火物に関するものである。TECHNICAL FIELD The present invention relates to a molten metal holding furnace,
The present invention relates to an electrofused refractory material for refractory materials used in refining furnaces, vacuum degassing furnaces, etc., and refractory materials using the same.
【０００２】[0002]
【従来の技術】マグネシアは耐食性に優れた成分であ
り、焼結マグネシアや電融マグネシアを使用したマグネ
シアれんがが広く使用されている。しかし、マグネシア
原料は熱膨張率が大きく、また、粒自体が容易にへき開
によって割れる等の性質をもつため、耐スポーリング性
に劣るという欠点をもつ。2. Description of the Related Art Magnesia is a component having excellent corrosion resistance, and magnesia bricks using sintered magnesia and electro-melting magnesia are widely used. However, the magnesia raw material has a large coefficient of thermal expansion, and since the grains themselves have the property of being easily cracked by cleavage, they have the drawback of being poor in spalling resistance.
【０００３】耐食性を低下することなく、耐スポーリン
グ性を改良した耐火物として、マグネシアと天然のクロ
ム鉱とを組み合わせたダイレクトボンドマグクロれんが
や、電融マグクロ原料を使用したリボンドあるいはセミ
リボンドマグクロれんがも広く実用されている。As a refractory having improved spalling resistance without lowering corrosion resistance, a direct bond magcro brick in which magnesia and natural chrome ore are combined, or a ribboned or semi-ribboned material using an electromelting magcro raw material. Maguro brick is also widely used.
【０００４】更に、耐食性の向上を目的に、ＭｇＯとＣ
ｒ2Ｏ3成分とを電融したピクロクロマイト原料も開発さ
れ、実用に供されている。また、マグネシア−アルミナ
スピネルを添加または生成させたマグネシア−スピネル
質耐火物はより優れた耐スポーリング性を有している。Further, for the purpose of improving the corrosion resistance, MgO and C
A picrochromite raw material in which an r 2 O 3 component is electrofused is also developed and put into practical use. Further, the magnesia-spinel refractory material to which magnesia-alumina spinel is added or formed has more excellent spalling resistance.
【０００５】[0005]
【発明が解決しようとする課題】上述の通りマグクロれ
んがは、通常、マグネシア原料と天然クロム鉱を組み合
わせたり、電融マグクロ原料単味や、電融マグクロ原料
とクロム鉱及び／またはマグネシア原料を組み合わせて
使用している。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, magro bricks are usually a combination of a magnesia raw material and natural chrome ore, a pure electro-fused maguro raw material, or a combination of an electro-fused maguro raw material and chrome ore and / or magnesia raw material. I am using it.
【０００６】天然クロム鉱を用いたダイレクトボンドマ
グクロれんがは、一般にリボンド品より耐スポーリング
性に優れる。これは、れんが焼成中に形成されるクロム
鉱とマグネシアとの反応による２次スピネルによる結
合、及び２次スピネル生成時の膨張に起因する組織形成
の効果と考えられている。Direct-bonded magcro bricks using natural chrome ores are generally superior in spalling resistance to ribbon products. It is considered that this is due to the effect of binding by the secondary spinel due to the reaction between the chromium ore and magnesia which are formed during the firing of the brick, and the texture formation due to the expansion during the formation of the secondary spinel.
【０００７】しかしながら、天然クロム鉱は、近年、耐
火物用としての高品位品の産出量が減少し、入手可能な
クロム鉱の品位は低下する傾向にある。特に問題となる
のは、鉱石中に主としてＳｉＯ2等の不純成分を含む脈
石といわれる層が存在することである。脈石は、例えば
蛇紋石や緑泥石などの鉱物からなる。脈石は、比較的低
温から溶融し始めるため、耐火物全体の耐食性を低下し
てしまうという問題がある。また、脈石はクロム鉱石の
内部に連続的に層を成しているため、加熱によりクロム
鉱の粒を分断してしまう。このためクロム鉱の粒が割れ
て本来の粒としての亀裂の伝播の阻止等の役割を果たす
ことができなくなる。通常、このような問題点を回避す
るためには、てきるだけ不純成分の少ないクロム鉱を選
択的に使用しなければならない。しかし、不純物のない
天然クロム鉱は工業規模では入手できないので、クロム
鉱の使用量(れんが中の配合量)には限界があるのが実状
である。[0007] However, in recent years, natural chrome ores have tended to decrease in production of high-grade products for refractories, and the quality of available chrome ores tends to decrease. A particular problem is the presence of a layer called a gangue mainly containing impure components such as SiO 2 in the ore. The gangue is composed of minerals such as serpentine and chlorite. Since gangue begins to melt at a relatively low temperature, there is a problem that the corrosion resistance of the entire refractory material is reduced. Moreover, since the gangue is continuously layered inside the chrome ore, the chrome ore particles are divided by heating. For this reason, the grains of the chrome ore break, and it becomes impossible to fulfill the role of preventing the propagation of cracks as the original grains. Usually, in order to avoid such a problem, it is necessary to selectively use chrome ore containing less impure components. However, since natural chrome ore with no impurities is not available on an industrial scale, the actual amount of chrome ore used is limited (blending amount in bricks).
【０００８】一方、電融マグクロ原料は、クロム鉱とマ
グネシアあるいはこれらに他の成分を添加して電気溶融
させたものであり、通常マグネシア含有量はおよそ５０
％以上であり、一旦高温に加熱されているために充分に
２次スピネルを形成している。この原料を使用して作ら
れるリボンドマグクロれんがは、優れた耐食性と熱間強
度を有する。しかしながら、現在の市販の電融マグクロ
原料は、原料自体の耐スポーリング性が充分でなく、こ
れを用いた耐火物の耐スポーリング性も、ダイレクトボ
ンドれんがと比較して劣っていると言わざるを得ない。On the other hand, the electromelting magcro raw material is chrome ore and magnesia, or these are added with other components and electromelted, and usually the magnesia content is about 50.
%, The secondary spinel is sufficiently formed because it is once heated to a high temperature. The ribbon-type magcro brick made from this raw material has excellent corrosion resistance and hot strength. However, the current commercially available electromelting magcro raw material does not have sufficient spalling resistance of the raw material itself, and the spalling resistance of the refractory material using the raw material is inferior to that of the direct bond brick. I don't get.
【０００９】ピクロクロマイトは、Ｃｒ2Ｏ3とＭｇＯの
２成分からなるスピネル鉱物の一つであり、Ａｌ2Ｏ3や
Ｆｅ2Ｏ3をほとんど含有していない(１％未満)。かなり
純度の高いマグネシア源と酸化クロムとを原料に電融し
たもので、原料費が高価であり、しかもこの鉱物の融点
が高いため、製造時の溶融コストが高くなるという欠点
がある。また、ピクロクロマイト原料を用いた耐火物
は、極端に焼結性が低下するので、充分な焼結強度を与
えるためには、高温で長時間焼成する必要がある。Picrochromite is one of the spinel minerals consisting of two components, Cr 2 O 3 and MgO, and contains almost no Al 2 O 3 or Fe 2 O 3 (less than 1%). It is a fusion of a highly pure magnesia source and chromium oxide as raw materials. The raw material cost is high, and the melting point of this mineral is high, so the melting cost during manufacturing is high. Further, since the refractory material using the picromchromite raw material has extremely low sinterability, it is necessary to fire at high temperature for a long time in order to provide sufficient sinter strength.
【００１０】アルミナ−マグネシアスピネルは近年比較
的安価に供給されるようになり、耐スポーリング性改善
には大きな効果が見られるが、同時にスラグに対する耐
食性の低下も大きい。Alumina-magnesia spinel has been supplied relatively inexpensively in recent years, and a great effect can be seen in improving spalling resistance, but at the same time, the corrosion resistance against slag is greatly reduced.
【００１１】従来のダイレクトボンドマグクロれんが
と、リボンドマグクロれんがの違いについて検討する
と、ダイレクトボンドマグクロれんがは、マグネシアと
クロム鉱との反応で生成する２次スピネルの形成が、れ
んがの性質を支配している。即ち、クロム鉱は、Ｃｒ2
Ｏ3、ＦｅＯ、Ｆｅ2Ｏ3、Ａｌ2Ｏ3及びＭｇＯからなる
スピネル鉱物の集合体であり、これが加熱されることに
よってマグネシアと反応して２次スピネルを生成する。
２次スピネルによる結合及び２次スピネル生成時に形成
される組織が、耐スポーリング性向上に効果があると考
えられている。しかしながら、クロム鉱は前記したよう
な脈石を持ち、本質的な欠点を有する。Examining the difference between conventional direct bond magcro bricks and ribboned magcro bricks, direct bond magcro bricks are characterized by the formation of secondary spinel formed by the reaction between magnesia and chrome ore. Dominates. That is, chromium ore is Cr 2
It is an aggregate of spinel minerals composed of O 3 , FeO, Fe 2 O 3 , Al 2 O 3 and MgO, and when heated, it reacts with magnesia to generate a secondary spinel.
It is considered that the bond formed by the secondary spinel and the structure formed during the formation of the secondary spinel are effective in improving the spalling resistance. However, chromite has the gangue as described above and has an inherent drawback.
【００１２】一方、リボンドマグクロれんがは、優れた
熱間強度を示すにも拘わらず、耐スポーリング性は、同
等の成分構成のれんがで比較してみても、ダイレクトボ
ンドマグクロれんがより劣る。これは前記した通り電融
マグクロ原料そのものに起因していると考えられる。従
って、電融耐火材料自体の耐スポーリング性を高める必
要がある。On the other hand, although the ribboned magcro bricks have excellent hot strength, the spalling resistance is inferior to the direct bond magcro bricks when compared with bricks having the same composition. . It is considered that this is due to the electromelting magro raw material itself as described above. Therefore, it is necessary to enhance the spalling resistance of the electrofused refractory material itself.
【００１３】従って、本発明の目的は、従来の耐火材料
及びこれを用いた耐火物のもつ問題点、即ち、脈石等に
よる耐食性の低下、粒の割れ、あるいは電融した材料自
体の耐食性の低下、製造コストの上昇等を解消し、耐食
性が高く、且つ耐スポーリング性に優れる電融耐火材料
及びこれを用いた耐火物を提供することにある。Therefore, an object of the present invention is to solve the problems of conventional refractory materials and refractory materials using the same, namely, deterioration of corrosion resistance due to gangue, cracking of grains, or corrosion resistance of the electromelted material itself. It is an object of the present invention to provide an electrofused refractory material having high corrosion resistance and excellent spalling resistance, and a refractory material using the same, by eliminating the decrease and the increase in manufacturing cost.
【００１４】[0014]
【課題を解決するための手段】即ち、本発明の電融耐火
材料は、Ｃｒ2Ｏ3成分、Ａｌ2Ｏ3成分、Ｆｅ2Ｏ3成分及
びＭｇＯ成分を必須成分として含有してなり、且つ各成
分のモル比が、ＭｇＯ／(Ｃｒ2Ｏ3＋Ａｌ2Ｏ3＋Ｆｅ2Ｏ
3)≦１.５の範囲内にあることを特徴とする。That is, the electrofused refractory material of the present invention comprises Cr 2 O 3 component, Al 2 O 3 component, Fe 2 O 3 component and MgO component as essential components, and The molar ratio of each component is MgO / (Cr 2 O 3 + Al 2 O 3 + Fe 2 O
3 ) It is characterized in being in the range of ≦ 1.5.
【００１５】更に、本発明の耐火物は、前記電融耐火材
料を５〜８５重量％含有してなることを特徴とする。Further, the refractory material of the present invention is characterized by containing 5 to 85% by weight of the above-mentioned electrofused refractory material.
【００１６】[0016]
【発明の実施の形態】本発明者らは、クロム鉱と電融マ
グクロ材料との違いについて種々検討を行い、天然クロ
ム鉱のもつ特徴を保持しつつ、欠点を抑制し、且つ現状
の電融マグクロ材料の欠点を生じせしめない新しい電融
耐火材料の開発を行った。その結果、脈石を含む天然ク
ロム鉱をそのまま何の成分も調整せずに電融すると、脈
石を形成していた不純成分はもとのクロム鉱石における
層状に繋がった脈石の状態とは全く異なり、粒内の一部
分に固定された状態で存在することが判った。BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have made various studies on the difference between a chrome ore and an electromelting magcro material, and while maintaining the characteristics of natural chrome ore, suppressing the defects, We have developed a new fused refractory material that does not cause the defects of maguro materials. As a result, when the natural chrome ore containing gangue is electrofused without adjusting any components, the impure component forming the gangue is not in the state of the layered gangue in the original chrome ore. It was found that it was completely different and was fixed in a part of the grain.
【００１７】即ち、脈石成分は、電融された固まり(イ
ンゴット)の中において、結晶間に層状に分布している
のではなく、部分、部分に固まって集合しているため、
これを粉砕して耐火物用原料とする場合も、粉砕された
粒の内部に取り込まれることが多く、粒の表面に達して
いないことが多い。従って、熱衝撃を受けた場合でも天
然クロム鉱のような脈石に起因する粒の分断、割れは全
く生じることがないため、例えば本発明の電融耐火材料
の一つである電融されたクロム鉱(電融クロム鉱)とマグ
ネシア原料とを混合して成形、焼成した本発明のマグク
ロれんがは、天然クロム鉱とマグネシア原料とからなる
従来のダイレクトボンドマグクロれんがより大幅に熱間
強度が高く、更に優れた耐スポーリング性を有すること
が判った。That is, the gangue component is not distributed in layers between crystals in the electromelted mass (ingot), but is concentrated in parts and portions, so that
When this is crushed and used as a raw material for refractories, it is often taken into the inside of the crushed particles, and often does not reach the surface of the particles. Therefore, even if it is subjected to a thermal shock, no fragmentation or cracking of grains caused by a gangue such as natural chrome ore occurs at all, and therefore, for example, one of the electrofused refractory materials of the present invention is electrofused. A mixture of chrome ore (electrofused chrome ore) and a magnesia raw material is molded and fired, and the magcro brick of the present invention has a significantly higher hot strength than a conventional direct-bond magro brick made of natural chrome ore and a magnesia raw material. It was found to be high and to have excellent spalling resistance.
【００１８】更に、ＳｉＯ2等の耐スラグ性を低下させ
る脈石成分が、粒の内部に取り込まれた状態で存在する
ため、直接スラグに接する機会が大幅に減少するので、
耐食性の向上も大きいことが判った。Further, since the gangue component such as SiO 2 which deteriorates the slag resistance is present in the state of being taken into the inside of the grain, the chance of directly contacting the slag is greatly reduced.
It was found that the corrosion resistance was greatly improved.
【００１９】次に、このような本発明の電融耐火材料
と、従来の電融マグクロ材料とは、耐火材料として要求
される品質特性においてどのような点が決定的に異なる
のかを検討考察した。その結果、最も大きな違いは材料
を構成している結晶の違いであると考えられた。つま
り、従来の電融マグクロ原料は、マグネシアの結晶であ
るペリクレースを主体として、Ｃｒ2Ｏ3、Ａｌ2Ｏ3、Ｆ
ｅ2Ｏ3とＭｇＯとの化合物であるスピネル族鉱物を伴っ
た混合体である。従って、従来の電融マグクロ材料は、
マグネシアの性質が強いために、耐スポーリング性に劣
るのは当然のことと考えられる。これに対して、本発明
の電融耐火材料は、構成鉱物の主鉱物がスピネル族鉱物
及びその固溶体から形成されており、ペリクレース結晶
を実質上含まない。スピネル族鉱物はいずれもペリクレ
ースよりも熱膨張率が小さいので、もともと粒自体が熱
衝撃に対して割れにくい。しかも、前述したように、脈
石の問題を解消できる。Next, it was examined and considered what kind of point the electromelting refractory material of the present invention and the conventional electromelting magcro material differ decisively in the quality characteristics required as the refractory material. . As a result, the biggest difference was considered to be the difference in the crystals that make up the material. That is, the conventional electromelting magcro raw material is mainly composed of periclase, which is a crystal of magnesia, and contains Cr 2 O 3 , Al 2 O 3 , and F.
It is a mixture with a spinel group mineral that is a compound of e 2 O 3 and MgO. Therefore, the conventional electrofused magcro material is
Due to the strong nature of magnesia, it is natural that the spalling resistance is inferior. On the other hand, in the electrofused refractory material of the present invention, the main mineral of the constituent minerals is formed from the spinel group mineral and its solid solution, and substantially does not contain periclase crystals. Since all spinel group minerals have a smaller coefficient of thermal expansion than periclase, the particles themselves are not easily cracked by thermal shock. Moreover, as described above, the problem of gangue can be solved.
【００２０】即ち、本発明の電融耐火材料が従来の天然
クロム鉱や電融マグクロ材料と本質的に異なる点は、
脈石を有しないこと；及び主鉱物がスピネル族鉱物及
びその固溶体からなりペリクレースを実質上含まないこ
と、の２点に集約される。That is, the point that the electrofused refractory material of the present invention is essentially different from the conventional natural chrome ore and electrofused magcro material is that
There are no gangues; and the main mineral is a spinel group mineral and its solid solution and is substantially free of periclase.
【００２１】の脈石を有しないことは、出発原料を電
融すること自体で達成可能である。また、電融すること
によって脈石成分の分布が変わることで、粒の割れを防
止する効果は前記の通りである。The absence of gangue can be achieved by electromelting the starting material itself. In addition, the effect of preventing the cracking of grains is the same as described above, because the distribution of the gangue component is changed by electromelting.
【００２２】次に、について検討した。電融された粒
に、フリーのペリクレースを実質上存在させず、主鉱物
をスピネル族鉱物及びその固溶体から構成し、割れの生
じにくい粒を得るための必要条件は、結論的に、電融さ
れた材料において、Ｃｒ2Ｏ3、Ａｌ2Ｏ3、Ｆｅ2Ｏ3、Ｍ
ｇＯの各成分のモル比が、ＭｇＯ／(Ｃｒ2Ｏ3＋Ａｌ2Ｏ
3＋Ｆｅ2Ｏ3)≦１.５の関係を満たしていることが必要
であることが判った。なお、上記式において、Ｆｅ2Ｏ3
量は、ＦｅＯとして存在する酸化鉄をＦｅ2Ｏ3に換算し
て合計した量である。Next, the following was examined. The essential conditions for obtaining grains that are resistant to cracking are that electro-fused grains are substantially free of free periclase, and the main mineral is composed of spinel group minerals and their solid solutions. In other materials, Cr 2 O 3 , Al 2 O 3 , Fe 2 O 3 , M
The molar ratio of each component of gO is MgO / (Cr 2 O 3 + Al 2 O
It has been found that it is necessary to satisfy the relationship of 3 + Fe 2 O 3 ) ≦ 1.5. In the above formula, Fe 2 O 3
The amount is the total amount of iron oxide existing as FeO converted to Fe 2 O 3 .
【００２３】上記を満足するモル比であれば、フリーの
ペリクレースが生成しにくく、スピネル族鉱物及びその
固溶体を主体とした、割れの生じにくい粒を得ることが
可能であることが判った。また、上記式の値が１〜１.
５の範囲内では、電融後の粒にペリクレースが存在する
ことがあるが、主鉱物はスピネル族鉱物であり、ペリク
レースが粒の性質を実質上左右するほどではなく、全く
ペリクレースを含まないものとほぼ同様に取り扱うこと
が可能である。勿論、上記式の値が１以下となることに
よって、ペリクレース結晶を含有しなくなるので、より
好ましいと言える。It has been found that if the molar ratio satisfies the above, it is possible to obtain grains in which free periclase is unlikely to be produced and which is mainly composed of spinel group minerals and solid solutions thereof and which is less likely to crack. In addition, the value of the above formula is 1-1.
Within the range of 5, periclase may be present in the grain after electrofusion, but the main mineral is a spinel group mineral, and the periclase does not substantially affect the properties of the grain, and it does not contain periclase at all. It can be handled in almost the same way as. Of course, when the value of the above formula is 1 or less, the periclase crystal is not contained, which is more preferable.
【００２４】しかしながら、上記式の値が１.５を超え
ると、主鉱物がペリクレースから構成され、徐々にペリ
クレースの性質が現れ、熱膨張率が増大する傾向を示
し、また、へき開による割れが生じ易くなってくるので
好ましくない。However, when the value of the above formula exceeds 1.5, the main mineral is composed of periclase, the property of periclase gradually appears, the thermal expansion coefficient tends to increase, and cracking due to cleavage occurs. It is not preferable because it becomes easier.
【００２５】一方、上記式の値が小さくても、特に耐ス
ポーリング性には大きな影響がないが、電融耐火材料の
構成鉱物をスピネル族鉱物主体とするためにはＦｅ2Ｏ3
含有量を多くする必要があるため、スラグ成分によって
は耐食性が低下することがある。従って、実用的に好ま
しい上記式の値の下限は０.２程度であり、高耐食性を
保つためには上記式の値の下限は０.３程度であること
が更に好ましい。On the other hand, even if the value of the above formula is small, it does not particularly affect the spalling resistance, but in order to make the spinel group mineral the constituent minerals of the electrofused refractory material, Fe 2 O 3
Since it is necessary to increase the content, the corrosion resistance may decrease depending on the slag component. Therefore, the lower limit of the value of the above formula that is practically preferable is about 0.2, and the lower limit of the value of the above formula is more preferably about 0.3 in order to maintain high corrosion resistance.
【００２６】更に、上記式の条件を満たしていても、Ｃ
ｒ2Ｏ3成分、Ａｌ2Ｏ3成分、Ｆｅ2Ｏ3成分、ＭｇＯ成分
以外の不純成分が多いと、耐火材料としての耐火度や耐
食性等に問題が生じる場合がある。従って、本発明の電
融耐火材料では、Ｃｒ2Ｏ3＋Ａｌ2Ｏ3＋Ｆｅ2Ｏ3＋Ｍｇ
Ｏの合量が９０重量％以上であることが好ましい。Further, even if the above condition is satisfied, C
If there are many impure components other than the r 2 O 3 component, the Al 2 O 3 component, the Fe 2 O 3 component, and the MgO component, problems such as fire resistance and corrosion resistance as a refractory material may occur. Therefore, in the electrofused refractory material of the present invention, Cr 2 O 3 + Al 2 O 3 + Fe 2 O 3 + Mg
The total amount of O is preferably 90% by weight or more.
【００２７】更に、本発明の電融耐火材料における各成
分の最適値は、Ｃｒ2Ｏ3が１５〜６５重量％、Ａｌ2Ｏ3
が５〜５０重量％、Ｆｅ2Ｏ3が１〜３０重量％、ＭｇＯ
が１０〜３５重量％の範囲内である。Further, the optimum values of the respective components in the electrofused refractory material of the present invention are as follows: Cr 2 O 3 is 15 to 65% by weight, Al 2 O 3
5 to 50 wt%, Fe 2 O 3 to 1 to 30 wt%, MgO
Is in the range of 10 to 35% by weight.
【００２８】Ｃｒ2Ｏ3が１５重量％未満では耐食性の低
下が見られ、６５重量％を超えると電融溶解時の溶解性
が低下するために好ましくない。If Cr 2 O 3 is less than 15% by weight, the corrosion resistance is deteriorated, and if it exceeds 65% by weight, the solubility at the time of electromelting is deteriorated, which is not preferable.
【００２９】また、Ａｌ2Ｏ3が５重量％未満では耐スポ
ーリング性の改善効果が少なく、また、５０重量％を超
えると高塩基度スラグに対する耐食性が低下することが
ある。When Al 2 O 3 is less than 5% by weight, the effect of improving the spalling resistance is small, and when it exceeds 50% by weight, the corrosion resistance to high basicity slag may be deteriorated.
【００３０】更に、Ｆｅ2Ｏ3は必ずしも多くは必要では
なく、３０重量％を超えると耐食性や耐還元性の面で劣
るようになるが、電融時の溶解性やれんが製造時の焼結
の点で１重量％以上必要である。Further, a large amount of Fe 2 O 3 is not always necessary, and if it exceeds 30% by weight, the corrosion resistance and the reduction resistance become poor, but the solubility at the time of electrofusion and the sintering at the time of manufacturing bricks are deteriorated. From the point of, 1% by weight or more is necessary.
【００３１】また、ＭｇＯが３５重量％を超えると上記
式を満足するのが困難になり、フリーのペリクレースが
生じ易くなるために好ましくない。一方、１０重量％未
満であると、スピネル構造の結晶を成しがたく好ましく
ない。If MgO exceeds 35% by weight, it becomes difficult to satisfy the above expression, and free periclase is likely to occur, which is not preferable. On the other hand, if it is less than 10% by weight, it is difficult to form crystals having a spinel structure, which is not preferable.
【００３２】このような成分構成を有する本発明の電融
耐火材料は、実質的にＣｒ2Ｏ3成分、Ａｌ2Ｏ3成分、Ｆ
ｅ2Ｏ3成分、ＭｇＯ成分の４成分を含有する材料単独ま
たは１成分または２成分以上を含有する材料の混合物を
電融して製造することができるる。ここで、「実質的
に」とは、実際の出発原料が必ずしも同じ酸素配位数の
酸化物でなくても、酸化された状態でＣｒ2Ｏ3、Ａｌ2
Ｏ3、Ｆｅ2Ｏ3、ＭｇＯを形成するもののことを意味す
る。例えば、出発原料中でＦｅＯであっても酸化された
状態ではＦｅ2Ｏ3となるものも問題なく使用することが
できる。The electrofused refractory material of the present invention having such a constitution is substantially composed of Cr 2 O 3 component, Al 2 O 3 component and F.
It can be produced by electromelting a material containing four components of e 2 O 3 component and MgO component alone or a mixture of materials containing one component or two or more components. Here, “substantially” means that Cr 2 O 3 , Al 2 in an oxidized state is used even if the actual starting materials are not necessarily oxides having the same oxygen coordination number.
It means that it forms O 3 , Fe 2 O 3 , and MgO. For example, even FeO in the starting material can be used without any problem as it becomes Fe 2 O 3 in the oxidized state.
【００３３】更に、本発明の電融耐火材料は、天然クロ
ム鉱単独または天然クロム鉱にＣｒ2Ｏ3、Ａｌ2Ｏ3、Ｆ
ｅ2Ｏ3、ＭｇＯの１成分または２成分以上を含有する材
料を添加し、電融することにより製造することができ
る。Further, the electrofused refractory material of the present invention is a natural chrome ore or a natural chrome ore containing Cr 2 O 3 , Al 2 O 3 and F.
It can be manufactured by adding a material containing one component or two or more components of e 2 O 3 and MgO and electrofusing.
【００３４】耐火物用の天然クロム鉱は、通常Ｃｒ2Ｏ3
３０〜６０重量％、Ａｌ2Ｏ3１０〜３０重量％、Ｆｅ2
Ｏ3(ＦｅＯの換算分を含む)１３〜３０重量％、ＭｇＯ
１０〜２０重量％程度であり、先にも述べているよう
に、何の成分調整をすることなく電融することにより、
本発明の電融耐火材料を得ることができる。しかも、出
発原料であるもとの天然クロム鉱に脈石を含んでいて
も、本発明によれば、割れの問題を解決することができ
る。Natural chrome ores for refractories are usually Cr 2 O 3
30-60 wt%, Al 2 O 3 10~30 wt%, Fe 2
O 3 (including FeO equivalent) 13 to 30% by weight, MgO
It is about 10 to 20% by weight, and as described above, by performing electrofusion without adjusting any components,
The electrofused refractory material of the present invention can be obtained. Moreover, even if the original natural chrome ore, which is the starting material, contains gangue, the present invention can solve the problem of cracking.
【００３５】また、天然クロム鉱に、成分を調整する目
的で単一あるいは複合酸化物材料を混合して電融するこ
とも可能である。例えば、Ｃｒ2Ｏ3値が高く、Ａｌ2Ｏ3
含有量の少ない天然クロム鉱に、耐スポーリング性を更
に高める目的で、アルミナ材料を加えて電融した電融耐
火材料を得ることも可能であり、実用的に非常に有効で
ある。It is also possible to mix natural ore chrome ore with a single or complex oxide material for the purpose of adjusting the components and to perform electrofusion. For example, the Cr 2 O 3 value is high, and Al 2 O 3 is
It is possible to obtain an electrofused refractory material by electrofusing an alumina material to a natural chrome ore having a small content for the purpose of further enhancing the spalling resistance, which is very effective in practice.
【００３６】勿論、単一の純度の高い酸化物を混合して
電融しても、本願の目的とする電融耐火材料が得られる
が、それぞれの出発原料が高価となるため、できるだけ
天然クロム鉱を使用して必要があれば成分を調整するた
めに純度の高い酸化物を添加して電融する方法が良い。Of course, even if a single high-purity oxide is mixed and electro-melted, the electro-melting refractory material aimed at by the present application can be obtained, but since each starting material is expensive, natural chrome is possible. It is preferable to use an ore and add an oxide of high purity to adjust the components, if necessary, and perform electrofusion.
【００３７】本発明の電融耐火材料に使用される出発原
料としては、通常の耐火物用天然クロム鉱以外に、Ｃｒ
2Ｏ3源としては顔料用等の酸化クロムや耐火物用よりも
Ｃｒ2Ｏ3値の高い冶金用クロム鉱などが、Ａｌ2Ｏ3源と
しては仮焼アルミナ、水酸化アルミニウム、ボーキサイ
ト、アルミナ頁岩、アルミニウム精錬時のスラッジやス
ケールなどが、Ｆｅ2Ｏ3源としては各種のベンガラなど
が、ＭｇＯ源としてはマグネシアクリンカー、軽焼マグ
ネシア、炭酸マグネシウム、水酸化マグネシウムなどが
使用される。これら以外でも、マグクロれんが、マグネ
シアれんが、アルミナ質れんが、スピネル質れんが等の
れんが屑を有効に活用することも可能であり、また、も
ともと脈石成分の多い低品位のクロム鉱と調整成分源と
を組み合わせるなど、出発原料の入手のし易さやコスト
の面から調整が可能である。勿論、予め各成分値は充分
に把握しておかなければならないことは言うまでもな
い。As a starting material used for the electrofused refractory material of the present invention, in addition to ordinary natural chrome ore for refractory, Cr is used.
The 2 O 3 source is chromium oxide for pigments and the like, and the chromium ore for metallurgy having a higher Cr 2 O 3 value than that for refractories, and the Al 2 O 3 source is calcined alumina, aluminum hydroxide, bauxite, alumina. Shale, sludge and scale during aluminum refining, various iron oxides as an Fe 2 O 3 source, magnesia clinker, light burned magnesia, magnesium carbonate, magnesium hydroxide and the like are used as MgO sources. Other than these, it is also possible to effectively utilize brick scraps such as magcro brick, magnesia brick, alumina brick, spinel brick, etc. It is possible to make adjustments in terms of availability and cost of starting materials, such as by combining. Of course, it goes without saying that each component value must be sufficiently grasped in advance.
【００３８】さて、このようにして得られる本発明の電
融耐火材料を用いて製造される本発明の耐火物は、当然
のことながら、本発明の電融耐火材料のもつ長所をその
まま受け継ぐことができる。即ち、脈石がないので耐ス
ポーリング性に優れ、また、脈石成分等の不純成分が粒
の表面に露出していることがほとんどないので、過度な
焼結が生じにくく、安定した焼結性が得られ、耐食性に
優れた耐火物を得ることができる。The refractory material of the present invention produced by using the thus obtained electromelting refractory material of the present invention naturally inherits the advantages of the electrofusion refractory material of the present invention. You can That is, since there is no gangue, it is excellent in spalling resistance, and since impure components such as gangue components are rarely exposed on the surface of the particles, excessive sintering is unlikely to occur and stable sintering is possible. It is possible to obtain a refractory having good corrosion resistance and excellent corrosion resistance.
【００３９】耐食性、耐スポーリング性において、本発
明の電融耐火材料の特徴を明確にするためには、本発明
の耐火物中における電融耐火材料の使用量は５〜８５重
量％の範囲内が好ましい。電融耐火材料の使用量が５重
量％未満であると、耐スポーリング性向上の効果が明確
ではない、一方、該使用量が８５重量％を超えると耐火
物の焼結性が低下してくるので、結合組織の脆弱化が生
じることがあり好ましくない。最も良い範囲は１０〜７
５重量％である。In order to clarify the characteristics of the electrofused refractory material of the present invention in terms of corrosion resistance and spalling resistance, the amount of the electrofused refractory material used in the refractory material of the present invention is in the range of 5 to 85% by weight. Is preferred. If the amount of the electrofused refractory material used is less than 5% by weight, the effect of improving the spalling resistance is not clear. On the other hand, if the amount used exceeds 85% by weight, the sinterability of the refractory material decreases. Therefore, the connective tissue may be weakened, which is not preferable. The best range is 10-7
5% by weight.
【００４０】本発明の耐火物において、本発明の電融耐
火材料以外として、少なくともマグネシアを用いること
が好ましい。マグネシアと本発明の電融耐火材料とを加
熱焼成により反応させ、２次スピネルを形成させること
により、ダイレクトボンドと同様の強固な結合をなし、
且つリボンドれんがのような緻密な結合組織を得ること
が可能となる。これにより、従来のリボンドでもダイレ
クトボンドでもない、両者を複合した更に優れた耐火物
が得られるものである。マグネシアは、１０〜９５重量
％、好ましくは１５〜９０重量％の範囲内で使用するこ
とが好ましい。In the refractory material of the present invention, it is preferable to use at least magnesia other than the electrofused refractory material of the present invention. By forming a secondary spinel by reacting magnesia with the electromelting refractory material of the present invention by heating and firing, a strong bond similar to a direct bond is formed,
In addition, it becomes possible to obtain a dense connective tissue such as a ribbon brick. This makes it possible to obtain a more excellent refractory material that is a composite of both, which is neither conventional ribbon bonded nor direct bond. Magnesia is preferably used in the range of 10 to 95% by weight, preferably 15 to 90% by weight.
【００４１】更に、本発明の耐火物には、その他、従来
からの耐火物用クロム鉱、電融及び焼結マグクロ原料、
電融及び焼結スピネル原料、アルミナ原料、ジルコニア
原料などを添加使用してもよく、微粉部に酸化クロムや
アルミナ、チタニアを添加しても良い。なお、これらの
原料の使用量は１〜８５重量％、好ましくは２〜７５重
量％の範囲内である。Further, in addition to the refractory material of the present invention, other conventional refractory chromium ores, electromelted and sintered magcro raw materials,
Electromelting and sintering spinel raw material, alumina raw material, zirconia raw material and the like may be added and used, and chromium oxide, alumina and titania may be added to the fine powder portion. The amount of these raw materials used is in the range of 1 to 85% by weight, preferably 2 to 75% by weight.
【００４２】また、本発明の耐火物には、リグニン類、
糖類、澱粉類、硫酸マグネシウム、メチルセルロース
類、フェノール樹脂、酢酸ビニル等のエマルジョン、ア
ルミナセメント、燐酸塩、珪酸塩のような結合剤や、炭
酸リチウム、消石灰、各種カルボン酸等のような調整剤
を添加することも可能である。The refractory material of the present invention includes lignin,
Emulsions of sugars, starches, magnesium sulfate, methylcelluloses, phenolic resins, vinyl acetate, etc., binders such as alumina cement, phosphates, silicates, and regulators such as lithium carbonate, slaked lime, various carboxylic acids, etc. It is also possible to add.
【００４３】なお、本発明の耐火物は、例えば不定形耐
火物、不焼成れんが、焼成れんが等の形態で使用するこ
とができる。不定形耐火物の場合、通常の各施工法に適
した粒度に調整したものを使用することができる。な
お、本発明の電融耐火材料は、水や通常の結合剤や調整
剤に対して安定であるので、どのような粒度でも問題な
く使用できる。The refractory material of the present invention can be used in the form of, for example, an irregular shaped refractory material, an unfired brick, or a fired brick. In the case of an irregular shaped refractory, it is possible to use a refractory that is adjusted to a particle size suitable for each ordinary construction method. In addition, since the electrofused refractory material of the present invention is stable against water and ordinary binders and modifiers, it can be used in any particle size without any problem.
【００４４】また、不焼成れんがの場合にも同様である
が、本発明の電融耐火材料以外にマグネシアを使用すれ
ば、本発明の耐火物の使用中の昇温によって膨張性を示
すので、加熱後線変化率をプラスに保つことが可能とな
り、不定形耐火物に生じ易い冷却時の亀裂を大幅に抑制
できるという特徴をもつ。The same applies to the case of non-fired bricks, but if magnesia is used in addition to the fusible refractory material of the present invention, the refractory material of the present invention exhibits expandability due to temperature rise during use. It is possible to keep the line change rate after heating to a positive value, and it is possible to significantly suppress cracks during cooling that are likely to occur in amorphous refractories.
【００４５】焼成れんがの場合には、通常の方法で、混
練、成形し、１５００〜１９００℃の温度で３時間以上
保持することが望ましい。焼成温度が１５００℃未満で
は本発明の電融耐火材料の焼結が充分に進行せず、焼成
れんがの品質が安定しないために好ましくない。一方、
焼成温度が１９００℃を超えるとエネルギーコストが増
大するが、それに見合う効果が得られない。焼成時の昇
温、降温の速度は、通常の焼成れんがと同様に、安定し
た製品を得るために３０〜１００℃／時間程度が望まし
い。In the case of a fired brick, it is desirable to knead and mold it by a usual method and hold it at a temperature of 1500 to 1900 ° C. for 3 hours or more. If the firing temperature is less than 1500 ° C., the electrofused refractory material of the present invention will not be sufficiently sintered and the quality of the fired brick will not be stable, which is not preferable. on the other hand,
If the firing temperature exceeds 1900 ° C., the energy cost will increase, but the effect commensurate with it will not be obtained. The rate of temperature increase / decrease during firing is preferably about 30 to 100 ° C./hour in order to obtain a stable product, as in the case of ordinary fired bricks.
【００４６】[0046]
実施例１ ２種の組成の異なるクロム鉱、マグクロれんが屑、及び
ほぼ単一成分からなる仮焼アルミナ、焼成マグネシア、
ベンガラ、酸化クロムを出発原料として電融耐火材料を
作成した。各出発原料の配合比、及びこれらを用いて作
成した電融耐火材料の化学成分値(重量％)、ＭｇＯ／
(Ｃｒ2Ｏ3＋Ａｌ2Ｏ3＋Ｆｅ2Ｏ3)モル比、Ｘ線回折試験
により同定された構成鉱物、琢磨片を顕微鏡下で観察し
た脈石の有無、１０００℃加熱時の膨張率、電融耐火材
料の粒のスポーリング試験結果について表１に示す。Example 1 Calcined alumina composed of two different compositions of chrome ore, magcro brick waste, and almost a single component, calcined magnesia,
An electrofused refractory material was prepared using red iron oxide and chromium oxide as starting materials. Mixing ratio of each starting material, and chemical composition value (wt%) of the electrofused refractory material prepared using these, MgO /
(Cr 2 O 3 + Al 2 O 3 + Fe 2 O 3 ) molar ratio, constituent minerals identified by X-ray diffraction test, presence or absence of gangue observed in polishing pieces under a microscope, expansion coefficient at 1000 ° C. heating, Table 1 shows the results of the spalling test of the particles of the fusion refractory material.
【００４７】表１中、粒のスポーリング試験結果は、
５.６ｍｍ以上の粒を１４００℃−水冷による熱変化を
２回与えた後に４.８ｍｍの篩目に残留した量を元の重
量に対する百分率で表したものであり、数値の小さい方
が割れにより細かくなった量が多いことを示すので、数
値が大きい方がスポーリング性が良好であることを示
す。なお、表１には、参考品として電融していないクロ
ム鉱Ａについても併記した。In Table 1, the results of the grain spalling test are as follows:
Particles of 5.6 mm or more are expressed as a percentage of the original weight by the amount remaining on the 4.8 mm sieve mesh after being subjected to heat change by water cooling at 1400 ° C. twice. Since the amount of fineness is large, the larger the number, the better the spalling property. In addition, Table 1 also shows the chromium ore A that is not electrofused as a reference product.
【００４８】[0048]
【表１】 [Table 1]
【００４９】表１から判るように、本発明の電融耐火材
料は主としてスピネル族鉱物からなる。本発明品４、５
及び６には、ごく少量のペリクレースが認められた。本
発明品の電融耐火材料はいずれも熱膨張率が比較的小さ
く、脈石の残存含有も全くない。粒のスピネル試験で
も、割れによる微細粒の生成は少ない。As can be seen from Table 1, the electrofused refractory material of the present invention mainly comprises spinel group minerals. Invention products 4, 5
In 6 and 6, a very small amount of periclase was observed. Each of the electromelting refractory materials of the present invention has a relatively small coefficient of thermal expansion and has no residual gangue. Even in the spinel test of grains, generation of fine grains due to cracking is small.
【００５０】比較品１及び２は、市販の電融マグクロ原
料の組成に近いものであり、比較品３は本発明の特徴で
あるＭｇＯ／(Ｃｒ2Ｏ3＋Ａｌ2Ｏ3＋Ｆｅ2Ｏ3)モル比を
市販品より小さく設定したものである。いずれの比較品
においても主鉱物はペリクレースであり、これにスピネ
ル族鉱物が随伴しているものである。従って、本発明品
と比べ１.３〜１.６倍程度も膨張率が大きい。粒のスポ
ーリング試験結果では、本発明品に比較しておよそ１／
３程度しか残留がなく、割れによる粒の微細化が認めら
れる。Comparative products 1 and 2 are close to the composition of the commercially available electro-fused maguro raw material, and comparative product 3 is MgO / (Cr 2 O 3 + Al 2 O 3 + Fe 2 O 3 ) which is a feature of the present invention. The molar ratio is set smaller than that of a commercial product. In each of the comparative products, the main mineral is periclase, which is accompanied by spinel group minerals. Therefore, the expansion coefficient is 1.3 to 1.6 times larger than that of the product of the present invention. The result of the spalling test of the grains is about 1 / th compared to the product of the present invention.
Only about 3 remains, and grain refinement due to cracking is observed.
【００５１】また、参考に示したクロム鉱は、本発明品
の電融耐火材料の出発原料として用いたクロム鉱Ａであ
るが、電融していないので、粒内に脈石を有するもので
あった。Further, the chromium ore shown as a reference is the chromium ore A used as the starting material of the electrofused refractory material of the present invention, but since it is not electrofused, it has gangue in the grains. there were.
【００５２】実施例２ 実施例１で得られた電融耐火材料のうち、本発明品１、
２、３、４、５及び６、比較品１及び３並びに参考品を
用いて焼成れんがを作成し、れんがとしての熱間曲げ強
度、耐スポーリング性及び耐スラグ侵食性を比較した。
れんがは、表２に示す配合比で原料を混合し、バインダ
ーとして糖蜜を２.５％添加し、混練後２.０トン／ｃｍ
2の圧力で２３０×１１４×１３０ｍｍの形状に成形し
た。２００℃で乾燥後約６０℃／時間の昇温速度で１８
００℃まで昇温し、６時間保持し、約６０℃／時間の降
温速度で冷却した。Example 2 Of the electrofused refractory materials obtained in Example 1, the product 1 of the present invention,
A fired brick was prepared using 2, 3, 4, 5 and 6, comparative products 1 and 3 and a reference product, and hot bending strength, spalling resistance and slag erosion resistance of the brick were compared.
For bricks, mix the raw materials in the mixing ratio shown in Table 2, add molasses 2.5% as a binder, and after kneading 2.0 ton / cm
It was molded under a pressure of 2 into a shape of 230 × 114 × 130 mm. After drying at 200 ℃, increase the temperature by about 60 ℃ / hour.
The temperature was raised to 00 ° C., maintained for 6 hours, and cooled at a temperature lowering rate of about 60 ° C./hour.
【００５３】こうして作成したれんがを、熱間曲げ強度
測定用には、４０×４０×１６０ｍｍに、スポーリング
試験用には４０×４０×４０ｍｍの大きさに切断加工し
て試料とした。熱間曲げ強度は、１４００℃に加熱した
電気炉中に投入、１５分間加熱した後、電気炉から取り
出し、３分間水冷することを１サイクルとしたスポーリ
ング試験を実施した。表２には、４個の試料についての
割れによる破壊に到るまでの回数の平均値を示した。回
数の多い方が割れにくく、耐スポーリング性に優れるこ
とを示す。耐スラグ侵食性は、回転ドラム法により、Ｃ
／Ｓ＝１.５のスラグを用いて１６５０〜１７００℃で
３時間侵食試験を行い、本発明品１１のれんがの侵食量
を１００として指数で示した。数値が小さい方が耐食性
に優れる。The brick thus produced was cut into a size of 40 × 40 × 160 mm for hot bending strength measurement and a size of 40 × 40 × 40 mm for spalling test to obtain a sample. For hot bending strength, a spalling test was carried out in which one cycle was to put in an electric furnace heated to 1400 ° C., heat for 15 minutes, then remove from the electric furnace and cool with water for 3 minutes as one cycle. Table 2 shows the average value of the number of times until breakage due to cracking was reached for four samples. The larger the number of times, the more difficult it is to break, and the better the spalling resistance. Slag erosion resistance is C by the rotary drum method.
A slag of /S=1.5 was used to perform an erosion test at 1650 to 1700 ° C. for 3 hours, and the erosion amount of the brick of the product 11 of the present invention was set as 100 and indicated by an index. The smaller the number, the better the corrosion resistance.
【００５４】[0054]
【表２】 [Table 2]
【００５５】表２から明らかなように、本発明品のれん
がは、いずれも熱間曲げ強度が高く、しかも、耐スポー
リング性に優れ、耐食性も良好であることが判る。比較
品１１のれんがを、本発明品１４及び１５のれんがと比
較すると、熱間強度や耐食性には大きな差はなく、本発
明品より幾分劣る程度であるが、耐スポーリング性は大
幅に低い。次に、比較品１２のれんがを、本発明品１２
及び１６のれんがと比較すると、熱間強度や耐食性には
大きな差はないが、耐スポーリング性は大幅に低い。更
に、従来品を本発明品１１のれんがと比較すると、脈石
に起因して熱間強度が低く、耐スポーリング性もやや劣
り、耐食性は本発明品１１のれんがより２０％近く悪
い。As is clear from Table 2, all of the bricks of the present invention have high hot bending strength, excellent spalling resistance, and good corrosion resistance. When the bricks of comparative product 11 are compared with the bricks of the present invention products 14 and 15, there is no significant difference in hot strength or corrosion resistance, and although it is somewhat inferior to that of the present invention product, the spalling resistance is significantly improved. Low. Next, the brick of comparative product 12
There is no great difference in hot strength and corrosion resistance compared with the bricks of No. 16 and 16, but the spalling resistance is significantly low. Further, when the conventional product is compared with the brick of the product 11 of the present invention, the hot strength due to gangue is low, the spalling resistance is slightly inferior, and the corrosion resistance of the product 11 of the present invention is poor by about 20%.
【００５６】実施例３ 表３に示した配合(表１の本発明品及び比較品を使用)で
流し込み材を作成し、水を加えて混練後、４０×４０×
１６０ｍｍの型枠に流し込み成形し、約２０時間自然養
生後、１０５℃で２４時間乾燥することにより供試体を
得た。なお、いずれの配合にも、外掛で分散剤として燐
酸塩とナフタレンスルホン酸ホルマリン縮合物との混合
品を、調整剤としてクエン酸を添加した。得られた供試
体を実施例２と同様の方法で、耐スポーリング性と耐食
性の比較評価を行った。なお、耐食性指数は、比較品２
１を１００として表した。Example 3 A casting material was prepared with the composition shown in Table 3 (using the product of the present invention and the comparative product of Table 1), water was added, and the mixture was kneaded.
It was cast in a 160 mm frame, naturally cured for about 20 hours, and then dried at 105 ° C. for 24 hours to obtain a sample. In addition, a mixture of a phosphate and a naphthalenesulfonic acid formalin condensate was added as a dispersant and citric acid was added as an adjuster to each formulation. The obtained specimen was subjected to comparative evaluation of spalling resistance and corrosion resistance in the same manner as in Example 2. In addition, the corrosion resistance index is comparative product 2
1 was expressed as 100.
【００５７】[0057]
【表３】 [Table 3]
【００５８】本発明品２１は比較品２２と類似の配合構
成で、電融耐火材料だけが異なるものであり、また、本
発明品２２は比較品２２とほぼ同じ化学成分値となるよ
うに配合比率を調整したものである。比較品２１はマグ
ネシアを主体として電融耐火材料を含まないものであ
る。表３で明らかなように、本発明品の耐スポーリング
性は格段に良好であり、比較品の３倍以上の耐割れ性を
有することが判る。また、耐食性も良好である。The product 21 of the present invention has a composition similar to that of the comparative product 22 except for the electrofused refractory material, and the product 22 of the present invention is compounded so as to have substantially the same chemical composition values as the comparative product 22. The ratio is adjusted. Comparative product 21 is mainly made of magnesia and does not contain an electrofused refractory material. As is clear from Table 3, the spalling resistance of the product of the present invention is remarkably good, and it is clear that it has cracking resistance three times or more that of the comparative product. Moreover, the corrosion resistance is also good.
【００５９】[0059]
【発明の効果】本発明によれば、耐食性が高く且つ耐ス
ポーリング性に優れる電融耐火材料及びこれを用いた耐
火物を提供することができる。According to the present invention, it is possible to provide an electrofused refractory material having high corrosion resistance and excellent spalling resistance, and a refractory material using the same.
Claims (6)
成分及びＭｇＯ成分を必須成分として含有してなり、且
つ各成分のモル比が、ＭｇＯ／(Ｃｒ2Ｏ3＋Ａｌ2Ｏ3＋
Ｆｅ2Ｏ3)≦１.５の範囲内にあることを特徴とする電融
耐火材料。1. A Cr 2 O 3 component, an Al 2 O 3 component, Fe 2 O 3
Component and MgO component as essential components, and the molar ratio of each component is MgO / (Cr 2 O 3 + Al 2 O 3 +
An electrofused refractory material characterized by being within the range of Fe 2 O 3 ) ≦ 1.5.
る請求項１記載の電融耐火材料。2. The electrofused refractory material according to claim 1, wherein the main mineral of the constituent minerals is a spinel group mineral.
2Ｏ3成分が５〜５０重量％、Ｆｅ2Ｏ3成分が１〜３０重
量％、ＭｇＯ成分が１０〜３５重量％の範囲内にあり、
且つＣｒ2Ｏ3＋Ａｌ2Ｏ3＋Ｆｅ2Ｏ3＋ＭｇＯの合量が９
０重量％以上である請求項１または２記載の電融耐火材
料。3. A Cr 2 O 3 component of 15 to 65% by weight, Al
2 O 3 component is in the range of 5 to 50 wt%, Fe 2 O 3 component is in the range of 1 to 30 wt%, and MgO component is in the range of 10 to 35 wt%,
In addition, the total amount of Cr 2 O 3 + Al 2 O 3 + Fe 2 O 3 + MgO is 9
The electrofused refractory material according to claim 1 or 2, which is 0% by weight or more.
Ｆｅ2Ｏ3成分及びＭｇＯ成分の４成分を含有する材料単
独、または１成分または２成分以上を含有する材料の混
合物を電融して得られる請求項１ないし３のいずれか１
項記載の電融耐火材料。4. A substantially Cr 2 O 3 component, an Al 2 O 3 component,
4. A material containing 4 components of Fe 2 O 3 component and MgO component alone or obtained by electromelting a mixture of materials containing 1 component or 2 or more components.
The electrofused refractory material according to the item.
にＣｒ2Ｏ3成分、Ａｌ2Ｏ3成分、Ｆｅ2Ｏ3成分、ＭｇＯ
成分の１成分または２成分以上を含有する材料を添加し
てなる混合物を電融して得られる請求項１ないし４のい
ずれか１項記載の電融耐火材料。5. Natural chrome ore alone or natural chrome ore with Cr 2 O 3 component, Al 2 O 3 component, Fe 2 O 3 component, MgO
The electrofused refractory material according to any one of claims 1 to 4, which is obtained by electromelting a mixture obtained by adding a material containing one or more of the components.
電融耐火材料を５〜８５重量％含有してなる耐火物。6. A refractory material containing 5 to 85% by weight of the electrofused refractory material according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7226745A JPH0971477A (en) | 1995-09-04 | 1995-09-04 | Electrofused refractory material and refractory using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7226745A JPH0971477A (en) | 1995-09-04 | 1995-09-04 | Electrofused refractory material and refractory using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0971477A true JPH0971477A (en) | 1997-03-18 |
Family
ID=16849948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7226745A Pending JPH0971477A (en) | 1995-09-04 | 1995-09-04 | Electrofused refractory material and refractory using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0971477A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019518697A (en) * | 2016-05-19 | 2019-07-04 | レフラテクニック ホルディング ゲゼルシャフト ミット ベシュレンクテル ハフツングＲＥＦＲＡＴＥＣＨＮＩＫ Ｈｏｌｄｉｎｇ ＧｍｂＨ | Fireproof spinel granules suitable for elasticizing crude ceramic refractories, method of making and use thereof |
-
1995
- 1995-09-04 JP JP7226745A patent/JPH0971477A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019518697A (en) * | 2016-05-19 | 2019-07-04 | レフラテクニック ホルディング ゲゼルシャフト ミット ベシュレンクテル ハフツングＲＥＦＲＡＴＥＣＨＮＩＫ Ｈｏｌｄｉｎｇ ＧｍｂＨ | Fireproof spinel granules suitable for elasticizing crude ceramic refractories, method of making and use thereof |
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