JP2014084269A - Castable refractory for nonferrous metal refining vessel and precast block using the same - Google Patents
Castable refractory for nonferrous metal refining vessel and precast block using the same Download PDFInfo
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- JP2014084269A JP2014084269A JP2012249695A JP2012249695A JP2014084269A JP 2014084269 A JP2014084269 A JP 2014084269A JP 2012249695 A JP2012249695 A JP 2012249695A JP 2012249695 A JP2012249695 A JP 2012249695A JP 2014084269 A JP2014084269 A JP 2014084269A
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- magnesia
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- corrosion resistance
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- 229910052751 metal Inorganic materials 0.000 title abstract description 20
- 239000002184 metal Substances 0.000 title abstract description 20
- 238000007670 refining Methods 0.000 title abstract description 3
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 23
- 239000011029 spinel Substances 0.000 claims abstract description 23
- 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 20
- 239000002994 raw material Substances 0.000 claims abstract description 17
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims description 18
- 239000011819 refractory material Substances 0.000 claims description 10
- 238000005260 corrosion Methods 0.000 abstract description 24
- 230000007797 corrosion Effects 0.000 abstract description 24
- 238000004901 spalling Methods 0.000 abstract description 23
- 239000002893 slag Substances 0.000 abstract description 11
- 238000000465 moulding Methods 0.000 abstract description 4
- 238000010304 firing Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 20
- 239000011651 chromium Substances 0.000 description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 15
- 238000003723 Smelting Methods 0.000 description 15
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 14
- 239000000395 magnesium oxide Substances 0.000 description 10
- 239000011449 brick Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 229910000423 chromium oxide Inorganic materials 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 239000004568 cement Substances 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 239000006104 solid solution Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- -1 ferrous metals Chemical class 0.000 description 1
- 239000011451 fired brick Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000001294 propane Substances 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
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Abstract
Description
本発明は、耐食性と耐スポーリング性を必要とするアルミニウム以外の非鉄金属製錬容器用ＭｇＯ−Ａｌ２Ｏ３−Ｃｒ２Ｏ３質キャスタブル耐火物、及びそれを用いたプレキャストブロックに関するものである。The present invention relates to a MgO—Al 2 O 3 —Cr 2 O 3 castable refractory for non-ferrous metal smelting vessels other than aluminum that requires corrosion resistance and spalling resistance, and a precast block using the same. .
Ａｌを除く非鉄金属製錬におけるスラグは、メタル中のカーボン量が高いため、一般的に、高ＦｅＯで、かつＣａＯ／ＳｉＯ２のモル比が低い。このような、非鉄金属製錬容器の稼働環境下では、マグネシア・クロム（マグ・クロ）質塩基性煉瓦が適性材料だとされ、長年広く使用されて来た。Since slag in non-ferrous metal smelting excluding Al has a high carbon content in the metal, it is generally high FeO and has a low molar ratio of CaO / SiO 2 . In such an operating environment for non-ferrous metal smelting vessels, magnesia-chromium basic brick is considered to be a suitable material and has been widely used for many years.
又、従来より、非鉄金属製錬容器には、大量の異型煉瓦が使用されていた。通常、異型煉瓦は人手による手打ち成型で制作されていた。Conventionally, a large amount of irregular bricks has been used for non-ferrous metal smelting vessels. Typically, odd-shaped bricks were produced by hand-made molding.
マグ・クロ質塩基性煉瓦に代わる材料として、特許文献１にはＣａＯ−ＭｇＯ−ＺｒＯ２質耐火物が非鉄金属製錬用ＦｅＯ−ＳｉＯ２系スラグに対して優れた耐食性と耐スポーリング性を示すと開示されている。As an alternative to mag-chromic basic bricks, Patent Document 1 discloses that CaO-MgO-ZrO 2 refractory has excellent corrosion resistance and spalling resistance against FeO-SiO 2 slag for non-ferrous metal smelting. It is disclosed to show.
特許文献２にはＡｌ２Ｏ３−Ｃｒ２Ｏ３−ＺｒＯ２質の非鉄金属精錬用耐火物が提案されている。Patent Document 2 proposes a non-ferrous metal refining refractory of Al 2 O 3 —Cr 2 O 3 —ZrO 2 quality.
特許文献３にはＡｌ２Ｏ３−ＳｉＯ２−Ｓｉ３Ｎ４質非鉄金属用キャスタブル耐火物が提案されている。Patent Document 3 proposes a castable refractory for Al 2 O 3 —SiO 2 —Si 3 N 4 nonferrous metal.
近年、ＭｇＯ−Ａｌ２Ｏ３−Ｃｒ２Ｏ３系材料が注目されている。本発明に関係するＭｇＯ−Ａｌ２Ｏ３−Ｃｒ２Ｏ３系材料の従来技術を以下に示す。In recent years, MgO—Al 2 O 3 —Cr 2 O 3 -based materials have attracted attention. The prior art of the MgO—Al 2 O 3 —Cr 2 O 3 material related to the present invention is shown below.
特許文献４には、スラグに対する耐浸食性に優れたクロム固溶スピネルクリンカー、特許文献５には、鉄鋼設備での耐食性と耐スポーリング性に優れた、クロム固溶スピネルクリンカーを主原料とする不定形耐火物、特許文献６には、製鋼、セメント及びガラスの分野における耐食性、耐浸透性および耐熱スポーリング性に優れた、ＭｇＯ−Ａｌ２Ｏ３系スピネル質原料と酸化クロムを主原料とする耐火れんが、特許文献７にはＡｌ２Ｏ３とＭｇＯとＣｒ２Ｏ３およびＺｒＯ２を複合させた溶融炉用耐火物、特許文献８には酸化クロムとスピネル粒子を主成分とする溶融炉用耐火物が、それぞれ開示されている。Patent Document 4 has a chromium solid solution spinel clinker excellent in corrosion resistance to slag, and Patent Document 5 has a chromium solid solution spinel clinker excellent in corrosion resistance and spalling resistance in steel facilities. In the amorphous refractory, Patent Document 6, MgO—Al 2 O 3 spinel material and chromium oxide, which are excellent in corrosion resistance, penetration resistance and heat spalling property in the fields of steelmaking, cement and glass, are mainly used. Patent Document 7 discloses a refractory for a melting furnace in which Al 2 O 3 , MgO, Cr 2 O 3 and ZrO 2 are combined, and Patent Document 8 discloses a melting furnace mainly composed of chromium oxide and spinel particles. Refractories for use are disclosed respectively.
又、本発明に関係する電融クロミアを主原料とするキャスタブル耐火物を開示したものとして特許文献９がある。Further, Patent Document 9 discloses a castable refractory using electrofused chromia as a main raw material related to the present invention.
しかしながら、特許文献１及び２に開示されている耐火物はＺｒＯ２を含有するので、ＺｒＯ２の鉱物変態の関係で耐スポーリング性が十分でない。However, refractories disclosed in Patent Documents 1 and 2 because it contains ZrO 2, is not sufficient spalling resistance in relation to mineral transformation ZrO 2.
特許文献３に開示されているキャスタブル耐火物及びプレキャストブロックはアルミナ・シリカ系原料を主原料としているので、スラグ中のＦｅＯと、ＦｅＯ−ＳｉＯ２とかＦｅＯ−Ａｌ２Ｏ３等の低融物を生成するため、耐食性に問題がある。Since the castable refractories and precast blocks disclosed in Patent Document 3 are mainly made of an alumina / silica-based raw material, a low-melting material such as FeO in slag, FeO-SiO 2 or FeO-Al 2 O 3 is used. Since it produces | generates, there exists a problem in corrosion resistance.
特許文献４，５に開示されているような、クロム固溶スピネルクリンカーを含有させただけの耐火物は耐スポーリング性が不十分である。As disclosed in Patent Documents 4 and 5, a refractory material containing only a chromium solid solution spinel clinker has insufficient spalling resistance.
特許文献６，７，８に開示されているＭｇＯ−Ａｌ２Ｏ３・Ｃｒ２Ｏ３系材料は、いずれも粉末の酸化クロムを、比較的に大量に含有させているので、耐スポーリング性に問題がある。微粉酸化クロムは、高温になると、他の微粉原料と合体して急速に焼結し、耐スポーリング性を低下させる。Since all MgO—Al 2 O 3 .Cr 2 O 3 materials disclosed in Patent Documents 6, 7, and 8 contain a relatively large amount of powdered chromium oxide, they are resistant to spalling. There is a problem. When the fine powdered chromium oxide reaches a high temperature, it coalesces with other fine powder raw materials and rapidly sinters, reducing the spalling resistance.
特許文献９に開示されている電融クロミアを大量に含有させた材料は、耐食性に問題は無いが、耐スポーリング性に劣る。A material containing a large amount of electrofused chromia disclosed in Patent Document 9 has no problem in corrosion resistance, but is inferior in spalling resistance.
従って、本発明の目的は、上記の従来の非鉄金属製錬容器用耐火物の問題点を解消し、非鉄金属製錬用ＦｅＯ−ＳｉＯ２系スラグに対して、優れた耐食性と耐スポーリング性を有する材料を提供すると共に、従来の非鉄金属製錬容器用異型耐火物の制作費が嵩むという問題を解消することにある。Therefore, the object of the present invention is to solve the above-mentioned problems of conventional refractories for non-ferrous metal smelting vessels, and to provide excellent corrosion resistance and spalling resistance to FeO-SiO 2 slag for non-ferrous metal smelting. In addition to providing a material having the above, there is a need to eliminate the problem of increasing the production costs of conventional refractories for non-ferrous metal smelting vessels.
本発明者は、上記問題を解決すべく鋭意研究・検討を行った。その結果、マグネシア・アルミナ系スピネル原料と電融クロミアを複合使用することにより、非鉄金属製錬用ＦｅＯ−ＳｉＯ２系スラグに対して優れた耐食性と耐スポーリング性を具有する材料が得られることを見出した。The present inventor has intensively studied and studied to solve the above problems. As a result, it is possible to obtain a material having excellent corrosion resistance and spalling resistance against FeO-SiO 2 slag for non-ferrous metal smelting by combining the use of magnesia / alumina-based spinel raw material and electrofused chromia. I found.
（１） 本発明は上記知見に基づきなされたものであり、その要旨は以下のとおりである。焼結および／または電融マグネシア・アルミナ系スピネルと電融クロミアを主原料とするキャスタブル耐火物。
（２） 上記（１）のキャスタブル耐火物を目的と用途に応じた枠に鋳込んで、硬化後に脱型、乾燥するか、または更に焼成することにより得られるプレキャストブロック。(1) This invention is made | formed based on the said knowledge, The summary is as follows. Castable refractories mainly made of sintered and / or fused magnesia / alumina spinel and fused chromia.
(2) A precast block obtained by casting the castable refractory according to (1) above into a frame according to the purpose and application, followed by demolding, drying or further firing after curing.
本発明に係るＭｇＯ−Ａｌ２Ｏ３−Ｃｒ２Ｏ３質キャスタブル耐火物、及びそれを用いたプレキャストブロックは、高ＦｅＯで、かつＣａＯ／ＳｉＯ２のモル比が低い、Ａｌ以外の非鉄金属製錬用スラグに対して、優れた耐食性と耐スポーリング性を示すので、従来のマグ・クロ質煉瓦に代替可能である。また、このプレキャストブロックは従来の異型手打ち成型煉瓦の代替となり得る。The MgO—Al 2 O 3 —Cr 2 O 3 castable refractory according to the present invention and a precast block using the same are made of non-ferrous metals other than Al, which have high FeO and a low molar ratio of CaO / SiO 2 . It shows excellent corrosion resistance and spalling resistance against smelting slag, so it can be replaced with conventional mug / chromic bricks. In addition, this precast block can be an alternative to conventional atypical hand-cast bricks.
以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
本発明では焼結および／または電融マグネシア・アルミナ系スピネル原料と電融クロミアを主たる原料として使用する。スピネルはＭｇＯとＡｌ２Ｏ３がモル比１：１の理論組成のものが良い。理論組成のものは、フリーのＭｇＯを含まないのでスレーキングしにくい。フリーのＡｌ２Ｏ３を含まないので耐食性が良い。In the present invention, sintered and / or electrofused magnesia / alumina-based spinel material and electrofused chromia are used as main materials. A spinel having a theoretical composition of MgO and Al 2 O 3 in a molar ratio of 1: 1 is preferable. The theoretical composition does not contain free MgO and is difficult to slake. Corrosion resistance is good because it does not contain free Al 2 O 3 .
本発明のＭｇＯ−Ａｌ２Ｏ３−Ｃｒ２Ｏ３質キャスタブル耐火物、及びそれを用いたプレキャストブロックにおいて、マグネシア−アルミナ系スピネル原料の配合量は４５〜８０質量％が好ましい。電融クロミアの配合量は５〜４０質量％が好ましい。電融クロミア配合量が５重量％以下だと耐食性が悪い。４０％以上だと耐食性は良いが、耐スポーリング性と耐浸透性が低下する。In the MgO—Al 2 O 3 —Cr 2 O 3 castable refractory and the precast block using the same, the blending amount of the magnesia-alumina-based spinel material is preferably 45 to 80% by mass. The blending amount of electrofused chromia is preferably 5 to 40% by mass. When the amount of electrofused chromia is 5% by weight or less, the corrosion resistance is poor. If it is 40% or more, the corrosion resistance is good, but the spalling resistance and penetration resistance are lowered.
本発明のキャスタブル耐火物は、マグネシア−アルミナ系スピネル原料と電融クロミアの他に、酸化クロム微粉、アルミナ微粉、アルミナセメント、揮発シリカ、分散剤等を適宜使用することから成る。The castable refractory of the present invention comprises appropriately using chromium oxide fine powder, alumina fine powder, alumina cement, volatile silica, a dispersant, etc. in addition to the magnesia-alumina-based spinel raw material and electrofused chromia.
上記酸化クロム微粉は、特に限定されず、一般に市販されている純度９７質量％以上のものが好ましい。純度の低いものは耐食性を低下させる。酸化クロム微粉の配合量は１５％以下が好ましい。１５％以上配合すると、耐スポーリング性が低下する。The said chromium oxide fine powder is not specifically limited, The thing of 97 mass% or more generally marketed purity is preferable. Those with low purity reduce the corrosion resistance. The blending amount of chromium oxide fine powder is preferably 15% or less. When it is blended by 15% or more, the spalling resistance is lowered.
本発明のキャスタブル耐火物には、結合剤としてアルミナセメントを使用する。アルミナセメントは市販の一般的なものが使用できる。アルミナセメントの配合量は１〜１０質量％が好ましい。１質量％以下では、強度不足となり、１０質量％以上だと、ＣａＯ成分が増えて耐食性低下の原因となる。The castable refractory of the present invention uses alumina cement as a binder. As the alumina cement, a commercially available general cement can be used. As for the compounding quantity of an alumina cement, 1-10 mass% is preferable. If it is 1% by mass or less, the strength is insufficient, and if it is 10% by mass or more, the CaO component increases and causes a decrease in corrosion resistance.
本発明のキャスタブル耐火物は、施工時又は成型時の流動性を増大させ、添加水量を低下させるために分散剤を使用する。分散剤は特に限定されるものではなく、例えばトリポリリン酸ナトリウム、ヘキサメタリン酸ナトリウム等が使用できる。The castable refractory of the present invention uses a dispersant to increase the fluidity during construction or molding and to reduce the amount of water added. A dispersing agent is not specifically limited, For example, sodium tripolyphosphate, sodium hexametaphosphate etc. can be used.
クロム固溶マグネシア・アルミナ系スピネルクリンカーを主原料にしたキャスタブル耐火物に対比して、本発明のマグネシア・アルミナ系スピネル原料と電融クロミア原料を主原料に使用したキャスタブル耐火物は、二種の原料がそれぞれ、融点の高い安定な鉱物の状態に在るので、耐食性、耐スポーリング性が共に高い。クロム固溶マグネシア・アルミナ系スピネルクリンカーの場合、Ｃｒ２Ｏ３とＭｇＯとＡｌ２Ｏ３の三成分が作用しあって、より融点の低い状態になっているので、相対的に耐食性が劣る。Compared to the castable refractories made of chromium solid solution magnesia / alumina spinel clinker as the main material, the castable refractories using the magnesia / alumina spinel raw material and electrofused chromia material of the present invention as the main raw materials are of two types: Since each raw material is in a stable mineral state with a high melting point, both corrosion resistance and spalling resistance are high. In the case of chromium solid solution magnesia / alumina-based spinel clinker, the three components Cr 2 O 3 , MgO, and Al 2 O 3 act to have a lower melting point, so that the corrosion resistance is relatively inferior.
本発明のキャスタブル耐火物の粒度構成は、１．０ｍｍ以上が３０〜７０質量％、０．１ｍｍ以下が２５〜６０質量％の範囲内の一般的な粒度範囲を有するものでよい。The particle size constitution of the castable refractory of the present invention may have a general particle size range in which 1.0 mm or more is 30 to 70% by mass and 0.1 mm or less is 25 to 60% by mass.
本発明のキャスタブル耐火物は、該キャスタブル耐火物に対して外掛けで３．５〜７質量％の水を加えて混練し、施工することができる。施工時にバイブレーターを使用するのが望ましい。The castable refractory of the present invention can be applied by kneading the castable refractory by adding 3.5 to 7% by mass of water as an outer shell. It is desirable to use a vibrator during construction.
本発明のキャスタブル耐火物は、Ａｌを除く非鉄金属製錬容器に直接流し込み施工するだけでなく、目的と用途に応じた任意形状の枠に鋳込んで、硬化後に、脱型、乾燥するか、又は更に焼成することにより得られるプレキャストブロックとしても使用することができる。The castable refractory of the present invention is not only directly cast into a non-ferrous metal smelting vessel except for Al, but also cast into a frame of any shape according to the purpose and application, and after being cured, demolded, dried, Alternatively, it can also be used as a precast block obtained by further firing.
以下、本発明を実施例により詳細に説明する。
表２に示す配合割合で各原料成分を配合したキャスタブル耐火物に所定量の水を加えて混練し、振動テーブルの上にのせた２３０×１１４×６５ｍｍの型枠に流し込んで成型を行った。硬化後に脱枠して成型体を得た。使用した各種原料の化学成分を表１に示した。Hereinafter, the present invention will be described in detail with reference to examples.
A predetermined amount of water was added to and kneaded into a castable refractory compounded with each raw material component at a blending ratio shown in Table 2, and the mixture was cast into a 230 × 114 × 65 mm mold placed on a vibration table. The frame was removed after curing to obtain a molded body. The chemical components of the various raw materials used are shown in Table 1.
このようにして得た成型体を１１０℃で２４時間乾燥し、更に１４００℃で１０時間焼成することにより供試体を得た。The molded body thus obtained was dried at 110 ° C. for 24 hours, and further fired at 1400 ° C. for 10 hours to obtain a specimen.
表４に、実施例１〜４と比較例５〜７、及び従来例８として、非鉄金属製錬容器で従来使用されている手打ち成型によるマグ・クロ質焼成煉瓦の試験結果を示した。
試験方法は以下のとおりである。Table 4 shows the test results of mag-chromic fired bricks by hand-made molding conventionally used in non-ferrous metal smelting vessels as Examples 1 to 4, Comparative Examples 5 to 7, and Conventional Example 8.
The test method is as follows.
かさ比重及び見掛気孔率：ＪＩＳ Ｒ２２０５に準じて測定した。Bulk specific gravity and apparent porosity: Measured according to JIS R2205.
圧縮強さ：ＪＩＳ Ｒ２２０６に準じて測定した。Compressive strength: measured according to JIS R2206.
耐スポーリング性：供試体の１１４×６５ｍｍ面の先端から三分の一までを１５００℃に保持した炉内で１５分間保持し、次いで室温で１５分間強制空冷した。この操作を４０回限度で繰り返し、剥落に至るまでの回数で評価した。耐スポーリング性は剥落までのサイクル回数が多い方が良好である。Spalling resistance: The specimen was held for 15 minutes in a furnace maintained at 1500 ° C. from the tip of the 114 × 65 mm surface to one third, and then forced air cooled for 15 minutes at room temperature. This operation was repeated up to 40 times and evaluated by the number of times until peeling. The spalling resistance is better when the number of cycles until peeling is larger.
浸食試験及び浸透試験：ドラムの内側に供試体を内張りし、そのドラムを回転させながら、酸素・プロパンバーナで内張り試片を１４００℃まで昇温し、加熱する。そこへ、表３に示すＣ／Ｓ＝０．２の非鉄金属製錬用のスラグを投入し、１０時間の浸食試験を行った。試片の耐食性を、浸食により減った試片の厚み（ｍｍ）により評価し、耐浸透性はスラグの浸透深さにより評価した。なお、従来例８の溶損量及び浸透深さを１００とする指数で示した。指数の数値が小さいほど良い。Erosion test and penetration test: A specimen is lined on the inside of a drum, and while the drum is rotated, the liner specimen is heated to 1400 ° C. with an oxygen / propane burner and heated. The slag for nonferrous metal smelting of C / S = 0.2 shown in Table 3 was thrown there, and the erosion test for 10 hours was done. The corrosion resistance of the specimen was evaluated by the thickness (mm) of the specimen reduced by erosion, and the penetration resistance was evaluated by the penetration depth of the slag. In addition, it showed with the index | exponent which makes the amount of erosion and penetration depth of the prior art example 8 100. The smaller the index number, the better.
表４に示すように、焼結であれ、電融であれ、スピネルクリンカーと電融クロミアを併用した実施例１，２，３，４は、耐スポーリング性と耐食性の両方が良好である。As shown in Table 4, Examples 1, 2, 3, and 4 in which spinel clinker and electrofused chromia are used in combination, both sintered and electrofused, have both good spalling resistance and corrosion resistance.
スピネルクリンカーだけを配合した比較例５は耐食性が低いことが判る。電融クロミアだけを配合した比較例６は、耐食性は、極めて良好であるが、耐スポーリング性に問題があることが判る。クロム固溶スピネルクリンカーを主原料とする比較例７は、耐スポーリング性に劣ることが判る。It turns out that the comparative example 5 which mix | blended only the spinel clinker has low corrosion resistance. It can be seen that Comparative Example 6 containing only electrofused chromia has very good corrosion resistance but has a problem in spalling resistance. It turns out that the comparative example 7 which uses a chromium solid solution spinel clinker as a main raw material is inferior to spalling resistance.
従来より、長年にわたって非鉄金属製錬炉において使用されていた手打ち成型マグ・クロ質煉瓦に相当する従来例８は、実施例１，２，３，４に比較して、耐スポーリング性、耐食性とも悪いことがわかる。Conventional example 8, which corresponds to hand-cast molded mag / chromic bricks used in non-ferrous metal smelting furnaces for many years, is more resistant to spalling and corrosion than Examples 1, 2, 3 and 4. Both are bad.
本発明のＭｇＯ−Ａｌ２Ｏ３−Ｃｒ２Ｏ３質キャスタブル耐火物は耐スポーリング性が良好であり、高ＦｅＯかつ、低塩基度（低Ｃ／Ｓ）のスラグに対する耐食性が良好であるので、Ａｌを除く非鉄金属製錬炉の内張り耐火物として好適に使用することができる。又、プレキャストブロックとして制作すれば、従来の手打ち成型マグ・クロ煉瓦に代替し得る。The MgO—Al 2 O 3 —Cr 2 O 3 castable refractory of the present invention has good spalling resistance and high corrosion resistance against slag with high FeO and low basicity (low C / S). It can be suitably used as a refractory lining for non-ferrous metal smelting furnaces excluding Al. Moreover, if it is produced as a precast block, it can be replaced with a conventional hand-molded mug / black brick.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114180869A (en) * | 2021-12-24 | 2022-03-15 | 长兴兴鹰新型耐火建材有限公司 | Prefabricated block with sulfur and alkali resistance, wear resistance and quick assembly function |
| CN115385681A (en) * | 2022-08-29 | 2022-11-25 | 郑州瑞泰耐火科技有限公司 | Magnesium-aluminum-chromium spinel castable and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114180869A (en) * | 2021-12-24 | 2022-03-15 | 长兴兴鹰新型耐火建材有限公司 | Prefabricated block with sulfur and alkali resistance, wear resistance and quick assembly function |
| CN115385681A (en) * | 2022-08-29 | 2022-11-25 | 郑州瑞泰耐火科技有限公司 | Magnesium-aluminum-chromium spinel castable and preparation method thereof |
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