JP2018168014A - Unfired brick refractory and method for producing unfired brick refractory - Google Patents
Unfired brick refractory and method for producing unfired brick refractory Download PDFInfo
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- 239000011452 unfired brick Substances 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 48
- 239000011029 spinel Substances 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 29
- 239000011451 fired brick Substances 0.000 claims description 24
- 239000002893 slag Substances 0.000 claims description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 230000004907 flux Effects 0.000 claims description 6
- 238000007885 magnetic separation Methods 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000011819 refractory material Substances 0.000 description 47
- 230000007797 corrosion Effects 0.000 description 33
- 238000005260 corrosion Methods 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 31
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 24
- 229910010271 silicon carbide Inorganic materials 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910003465 moissanite Inorganic materials 0.000 description 12
- 238000005245 sintering Methods 0.000 description 11
- 239000011449 brick Substances 0.000 description 10
- 239000002245 particle 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 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Abstract
Description
本発明は、高炉樋に使用されていたＡｌ２Ｏ３、ＭｇＯ、ＳｉＣ、Ｃ質を含む耐火物を原料の一部として用いた不焼成れんが耐火物および不焼成れんが耐火物の製造方法に関する。 The present invention relates to an unfired brick refractory using a refractory containing Al 2 O 3 , MgO, SiC, and C, which has been used in a blast furnace, as a part of the raw material, and a method for producing the unfired brick refractory.
耐火物は、各種高温の炉等の内張りに使用されている。製鉄所においては、例えば、樋、溶鉄搬送容器や精錬容器などに用いられている。これらの耐火物は、溶銑もしくはスラグによって損耗し、規定回数使用されると、張り替えるために解体されている。解体された耐火物は、廃棄処分される場合が多いが、近年では、耐火物の原料の一部としてリサイクルする試みがなされている。 Refractories are used for linings of various high-temperature furnaces. In steelworks, it is used for, for example, dredging, molten iron transport containers, refining containers, and the like. These refractories are worn away by hot metal or slag and are demolished for replacement after being used a specified number of times. In many cases, dismantled refractories are discarded, but in recent years, attempts have been made to recycle them as a part of refractory raw materials.
例えば、特許文献１には、アルミナ・ろう石・炭化ケイ素・カーボン質を含む使用済耐火物を３ｍｍ以下の粒度に粉砕し、ろう石や炭化ケイ素を主成分とする不焼成れんが耐火物の原料の一部として、１０〜２０質量％配合した不焼成れんが耐火物が開示されている。 For example, Patent Document 1 discloses a raw material for unfired brick refractories containing a slaked stone or silicon carbide as a main component by pulverizing a used refractory containing alumina, wax, silicon carbide, and carbon. As a part of this, a non-fired brick refractory compounded with 10 to 20% by mass is disclosed.
また、特許文献２には、使用済耐火物に対して、一次の磁力選別を行なって地金を除去した後に破砕して篩分けし、さらに粒度毎に一次の磁力選別よりも大きな磁力で二次の磁力選別を行なって磁性体と非磁性体に分類し、当該非磁性体を耐火物原料に再利用する処理方法が開示されている。 In Patent Document 2, primary refractory material is subjected to primary magnetic sorting to remove the bare metal, then crushed and sieved, and each particle size has a larger magnetic force than the primary magnetic sorting. A processing method is disclosed in which the following magnetic separation is performed to classify the magnetic material and the non-magnetic material, and the non-magnetic material is reused as a refractory material.
しかしながら、従来のリサイクル技術は、あくまで、安価原料の利用や通常品と同等の特性を得ることを目的としており、使用済耐火物の特性を利用して、当該使用済耐火物を使用した耐火物の特性を向上させることは考えられていなかった。本発明は、使用済耐火物を再使用することで資源を有効活用し廃棄物を減少させるだけでなく、使用済耐火物を使用することで特性を向上させた不焼成れんが耐火物を提供することを目的とする。 However, the conventional recycling technology is only for the purpose of using inexpensive raw materials and obtaining the same characteristics as ordinary products, and using the properties of the used refractory, the refractory using the used refractory. It was not considered to improve the characteristics. The present invention provides a non-fired brick refractory whose properties are improved by using a used refractory as well as effectively reducing resources and reducing waste by reusing the used refractory. For the purpose.
このような課題を解決するための本発明の特徴は、以下の通りである。
（１）Ａｌ２Ｏ３、ＳｉＣおよびＣを含有する不焼成れんが耐火物であって、スピネルを含有する高炉樋の使用済耐火物を、１０質量％以上７０質量％以下の範囲内で含有する、不焼成れんが耐火物。
（２）前記高炉樋の使用済耐火物は、前記スピネルを１０質量％以上７０質量％以下の範囲内で含有する、（１）に記載の不焼成れんが耐火物。
（３）前記不焼成れんが耐火物は、さらにＢ２Ｏ３、Ｋ２Ｏ、Ｎａ２ＯおよびＰ２Ｏ５のガラス材料のうち１種類以上、および／または、非晶質シリカを０．５質量％以上２．０質量％以下の範囲内で含有する、（１）または（２）に記載の不焼成れんが耐火物。
（４）Ａｌ２Ｏ３、ＳｉＣおよびＣを含有する不焼成れんが耐火物の製造方法であって、スピネルを１０質量％以上７０質量％以下の範囲内で含有する高炉樋の使用済耐火物を１０質量％以上７０質量％以下の範囲内で含有し、Ｂ２Ｏ３、Ｋ２Ｏ、Ｎａ２ＯおよびＰ２Ｏ５のガラス材料のうち１種類以上、および／または、非晶質シリカを０．５質量％以上２．０質量％以下の範囲内で含有する耐火物原料に、バインダーを外掛けで１質量％以上４質量％以下の範囲内で加えて混練し、成型した後に乾燥させる、不焼成れんが耐火物の製造方法。
（５）使用後のメタルライン材を含む高炉樋を粉砕し、０．３テスラ未満の磁束密度で磁力選別し、さらに、０．３テスラ以上の磁束密度で磁力選別し、さらに、密度分離して、前記高炉樋の使用済耐火物を製造する、（４）に記載の不焼成れんが耐火物の製造方法。
The features of the present invention for solving such problems are as follows.
(1) Unfired brick containing Al 2 O 3 , SiC and C is refractory, and contains spent refractory of blast furnace containing spinel within a range of 10 mass% to 70 mass%. Unfired brick refractory.
(2) The unfired brick refractory according to (1), wherein the used refractory of the blast furnace hoe contains the spinel within a range of 10% by mass to 70% by mass.
(3) The non-fired brick refractory may further include at least one kind of glass material of B 2 O 3 , K 2 O, Na 2 O and P 2 O 5 and / or 0.5% of amorphous silica. The unfired brick refractory according to (1) or (2), which is contained within a range of mass% to 2.0 mass%.
(4) A method for producing an unfired brick refractory containing Al 2 O 3 , SiC and C, wherein a used refractory for a blast furnace containing spinel in a range of 10% by mass to 70% by mass 10% by mass or more and 70% by mass or less of one or more glass materials of B 2 O 3 , K 2 O, Na 2 O and P 2 O 5 and / or amorphous silica A refractory material contained in the range of 0.5% by mass or more and 2.0% by mass or less is added with a binder in the range of 1% by mass or more and 4% by mass or less, and kneaded, molded, and dried. , A method for producing unfired brick refractories.
(5) The blast furnace slag containing the metal line material after use is crushed, magnetically sorted with a magnetic flux density of less than 0.3 Tesla, further magnetically sorted with a magnetic flux density of 0.3 Tesla or higher, and further density separated. And the manufacturing method of the unfired brick refractory as described in (4) which manufactures the used refractory of the said blast furnace firewood.
本発明の不焼成れんが耐火物は、高炉樋として使用され、焼結反応が進行したスピネルを含むので、不焼成れんが耐火物の耐食性を向上させながら、耐スポール性の低下を抑制できる。また、本発明の不焼成れんが耐火物の製造方法の実施により、資源を有効活用しつつ、上述した特性を向上させた不焼成れんが耐火物を製造できる。 Since the unfired brick refractory of the present invention includes spinel that is used as a blast furnace and has undergone a sintering reaction, the deterioration of the spall resistance can be suppressed while improving the corrosion resistance of the unfired brick refractory. In addition, by implementing the method for producing an unfired brick refractory according to the present invention, it is possible to produce an unfired brick refractory with improved properties as described above while effectively utilizing resources.
高炉から出銑される溶銑は、転炉で精錬処理される前に溶銑成分を調整することを目的として溶銑予備処理される。溶銑予備処理は、溶銑搬送容器や溶銑鍋で実施される場合があり、そのような溶銑搬送容器や溶銑鍋の耐火物には、高い耐食性と、高い耐スポール性を兼ね備えることが求められる。 The hot metal discharged from the blast furnace is subjected to hot metal pretreatment for the purpose of adjusting the hot metal components before being refined in the converter. The hot metal preliminary treatment may be performed in a hot metal transport container or hot metal ladle, and the refractory material of such hot metal transport container or hot metal pan is required to have both high corrosion resistance and high spall resistance.
従来、溶銑搬送容器や溶銑鍋の耐火物には、アルミナ、炭化ケイ素、カーボン質の耐火物およびアルミナ、カーボン質の耐火物が用いられてきたが、これらの耐火物の耐食性および耐スポール性は未だ不十分である。スピネルは、アルミナよりもスラグに対する耐食性が高いことが知られているが、耐火物として長期間使用されると焼結反応により割れ、耐火物の耐スポール性を低下させるので用いられてこなかった。 Conventionally, alumina, silicon carbide, carbonaceous refractories and alumina, carbonaceous refractories have been used as refractories for hot metal transport containers and hot pots, but the corrosion resistance and spall resistance of these refractories are It is still insufficient. Although spinel is known to have higher corrosion resistance to slag than alumina, it has not been used because it cracks due to a sintering reaction when used as a refractory for a long period of time and reduces the spall resistance of the refractory.
高炉樋として使用された耐火物に含まれるスピネルは、溶銑および高炉スラグによって長期間加熱されて焼結反応が進行されているので、さらに耐火物として使用されても焼結反応はほとんど進行しない。発明者らはこの点に着目し、高炉樋として使用された耐火物のスピネルは、スラグに対する高い耐食性を有するとともに、耐火物の耐スポール性の低下を抑制できることを見出して本発明を完成させた。以下に本発明の実施形態を通じて本発明を説明する。 Since the spinel contained in the refractory used as the blast furnace slag is heated for a long time by the hot metal and the blast furnace slag and the sintering reaction proceeds, the sintering reaction hardly proceeds even when used as a refractory. The inventors focused on this point, and found that the refractory spinel used as a blast furnace slag has high corrosion resistance against slag and can suppress a decrease in spall resistance of the refractory, thereby completing the present invention. . Hereinafter, the present invention will be described through embodiments of the present invention.
図１は、高炉樋耐火物１０の断面図を示す。高炉樋耐火物１０は、メタルライン材１２と、スラグライン材１４とから構成される。高炉から出銑された溶銑１６および高炉スラグ１８は、高炉樋耐火物１０を通って溶銑搬送容器（不図示）へ移送される。 FIG. 1 shows a cross-sectional view of a blast furnace refractory 10. The blast furnace refractory 10 is composed of a metal line material 12 and a slag line material 14. The hot metal 16 and the blast furnace slag 18 discharged from the blast furnace are transferred to the hot metal transfer container (not shown) through the blast furnace refractory 10.
高炉樋耐火物１０において、メタルライン材１２は、図１に示すように、溶銑１６と高炉スラグ１８との界面が接するように高炉樋耐火物１０の下側に設けられる。また、スラグライン材１４は、高炉スラグ１８と空気との界面が接するように、高炉樋耐火物１０の上側に設けられる。一般的に、メタルライン材１２は、Ａｌ２Ｏ３を５０〜８０質量％含み、ＭｇＯを１０〜３０質量％含み、ＳｉＣを５〜２５質量％含み、Ｃを２〜１５質量％含む。また、スラグライン材１４は、Ａｌ２Ｏ３を１０〜３０質量％含み、ＳｉＣを３０〜７０質量％含み、Ｃを２〜１５質量％含む。ここで、メタルライン材に含有されるスピネルは、Ａｌ２Ｏ３：ＭｇＯの質量比が、６５：３５〜８５：１５の範囲内であれば、理論組成のスピネルでなくても構わない。 In the blast furnace refractory 10, the metal line material 12 is provided below the blast furnace refractory 10 so that the interface between the hot metal 16 and the blast furnace slag 18 is in contact with the blast furnace refractory 10 as shown in FIG. 1. The slag line material 14 is provided on the upper side of the blast furnace refractory 10 so that the interface between the blast furnace slag 18 and air is in contact therewith. Generally, metal line material 12 includes Al 2 O 3 50 to 80 wt%, MgO hints 10 to 30 mass%, SiC and containing 5 to 25 wt%, including C 2 to 15 wt%. Also, slag line member 14 includes Al 2 O 3 10 to 30 wt%, SiC and containing 30 to 70 wt%, including C 2 to 15 wt%. Here, the spinel contained in the metal line material may not be a spinel having a theoretical composition as long as the mass ratio of Al 2 O 3 : MgO is in the range of 65:35 to 85:15.
高炉樋耐火物１０は、予め定められた通銑量の溶銑が通った後に解体される。解体された使用済の高炉樋耐火物１０は、メタルライン材１２およびスラグライン材１４の区別なく粉砕される。少なくともスピネルを含有するメタルライン材１２を含む高炉樋が解体され、所定の粒度、例えば８ｍｍ以下の粒度になるまで粉砕された後に磁力選別される。磁力選別は２回行なわれ、１回目の磁力選別は０．３テスラ未満の磁束密度で行なわれ、２回目の磁力選別は０．３テスラ以上の磁束密度で行なわれる。磁力選別によって選別された非磁着物は、さらに密度分離されて高炉樋の使用済耐火物となる。なお、本実施形態において、８ｍｍ以下の粒度とは目開き８ｍｍの篩でふるい、篩下に篩分けされる粒度である。また、少なくともスピネルを含有するメタルライン材１２を含む高炉樋の粉砕は、例えば、粒度が１５ｍｍ以下になるまで粉砕されてもよく、１０ｍｍ以下になるまで粉砕されてもよい。 The blast furnace refractory 10 is disassembled after a predetermined amount of hot metal has passed. The dismantled used blast furnace refractory 10 is pulverized without distinction between the metal line material 12 and the slag line material 14. The blast furnace slag including the metal line material 12 containing at least spinel is dismantled and pulverized to a predetermined particle size, for example, a particle size of 8 mm or less, and then magnetically sorted. The magnetic separation is performed twice, the first magnetic separation is performed with a magnetic flux density of less than 0.3 Tesla, and the second magnetic separation is performed with a magnetic flux density of 0.3 Tesla or more. The non-magnetized material selected by the magnetic separation is further subjected to density separation to become a used refractory for the blast furnace. In the present embodiment, the particle size of 8 mm or less is a particle size that is sieved with a sieve having an opening of 8 mm and sieved under the sieve. Moreover, the pulverization of the blast furnace iron including the metal line material 12 containing at least spinel may be pulverized until the particle size becomes 15 mm or less, or may be pulverized until the particle size becomes 10 mm or less.
本実施形態に係るＡｌ２Ｏ３、ＳｉＣおよびＣを含有する不焼成れんが耐火物は、高炉から出銑される溶銑の予備処理が実施される溶銑搬送容器や溶銑鍋に用いられる。これら不焼成れんが耐火物の主な組成は、Ａｌ２Ｏ３を３０〜７０質量％含み、ＳｉＣを０〜１５質量％含み、Ｃを５〜２０質量％含む。また、このほかに、例えば、ＳｉＯ２を含む場合もある。 The unfired brick refractory containing Al 2 O 3 , SiC and C according to the present embodiment is used in a hot metal transport container or hot metal ladle in which hot metal pretreatment from the blast furnace is performed. The main composition of these unfired brick refractories includes 30 to 70% by mass of Al 2 O 3 , 0 to 15% by mass of SiC, and 5 to 20% by mass of C. In addition, for example, SiO 2 may be included.
本実施形態に係る不焼成れんが耐火物は、当該不焼成れんが耐火物の原料としてスピネルを含有する高炉樋の使用済耐火物を、不焼成れんが耐火物の質量に対して１０質量％以上７０質量％以下の範囲内で含有する。これにより、耐食性を高めながら、耐スポール性の低下が抑制された不焼成れんが耐火物にできる。なお、高炉樋の使用済耐火物の含有量を１０質量％未満にすると、スピネル含有量が少なくなり、不焼成れんが耐火物の耐食性向上効果が少なくなるので好ましくない。また、高炉樋の使用済耐火物の含有量を７０質量％より多くすると、不焼成れんが耐火物のＳｉＣ含有量が多くなりすぎて耐食性が低下するので好ましくない。 The unfired brick refractory according to this embodiment is a used refractory of a blast furnace containing spinel as a raw material of the unfired brick refractory, and is 10% by mass or more and 70% by mass with respect to the mass of the unfired brick refractory % Or less. Thereby, the non-fired brick in which the decrease in the spall resistance is suppressed while enhancing the corrosion resistance can be made into a refractory. If the content of the used refractory of the blast furnace is less than 10% by mass, the spinel content is decreased, and the effect of improving the corrosion resistance of the refractory is reduced. Further, if the content of the used refractory in the blast furnace is more than 70% by mass, unburned brick is not preferable because the SiC content of the refractory is excessively increased and the corrosion resistance is lowered.
また、不焼成れんが耐火物の原料として用いる高炉樋の使用済耐火物は、スピネルを１０質量％以上７０質量％以下の範囲内で含有する。高炉樋の使用済耐火物のスピネル含有量が１０質量％未満であると、スピネル含有量が少なくなり、不焼成れんが耐火物の耐食性向上効果が少なくなるので好ましくない。また、使用済耐火物のスピネル含有量が７０質量％より多くなると、不焼成れんが耐火物の耐スポール性が低下するので好ましくない。なお、高炉樋の使用済耐火物のスピネル含有量は、使用済耐火物を粉砕し、当該粉砕物を十分に混合させた後に測定してよい。 Moreover, the used refractory of the blast furnace fired used as a raw material of unfired brick refractory contains spinel in the range of 10 mass% or more and 70 mass% or less. When the spinel content of the used refractory of the blast furnace is less than 10% by mass, the spinel content is decreased, and unburned brick is not preferable because the effect of improving the corrosion resistance of the refractory is decreased. Further, if the spinel content of the used refractory is more than 70% by mass, unsintered brick is not preferable because the spall resistance of the refractory is lowered. In addition, you may measure the spinel content of the used refractory material of a blast furnace after grind | pulverizing a used refractory material and fully mixing the said pulverized material.
スピネルは、アルミナよりもスラグに対する耐食性が高いが、耐火物として長期間使用されると焼結反応により割れ、耐火物の耐スポール性を低下させる。しかしながら、高炉樋の使用済耐火物に含まれるスピネルは、溶銑および高炉スラグによって長期間加熱されて焼結反応が進行されているので、さらに加熱されたとしても焼結反応はほとんど進行しない。このため、高炉樋の使用済耐火物に含まれるスピネルを用いることで、不焼成れんが耐火物の耐スポール性の低下を抑制しながら、耐食性を向上できる。 Spinel has higher corrosion resistance to slag than alumina, but when used as a refractory for a long time, spinel breaks due to a sintering reaction and lowers the spall resistance of the refractory. However, since the spinel contained in the spent refractory of the blast furnace iron is heated for a long time by the hot metal and the blast furnace slag and the sintering reaction proceeds, the sintering reaction hardly proceeds even if further heated. For this reason, corrosion resistance can be improved by using the spinel contained in the used refractory material of a blast furnace iron, suppressing the fall of the spall resistance of unfired brick refractory material.
さらに、高炉樋の使用済耐火物に含まれるスピネルは、骨材間にＣやＳｉＣが存在している。不焼成れんが耐火物の原料として当該スピネルを用いた場合、骨材間に存在するＣやＳｉＣがスピネルの焼結を阻害する。このため、高炉樋の使用済耐火物に含まれるスピネルを用いることで、不焼成れんが耐火物の耐スポール性の低下を抑制しながら、耐食性を向上できる。 Furthermore, the spinel contained in the used refractories of the blast furnace iron contains C and SiC between aggregates. When the spinel is used as a raw material for non-fired brick refractory, C and SiC existing between the aggregates inhibit the spinel sintering. For this reason, corrosion resistance can be improved by using the spinel contained in the used refractory material of a blast furnace iron, suppressing the fall of the spall resistance of unfired brick refractory material.
本実施形態に係る不焼成れんが耐火物は、さらに、Ｂ２Ｏ３、Ｋ２Ｏ、Ｎａ２ＯおよびＰ２Ｏ５のガラス材料のうち１種類以上、および／または、非晶質シリカを０．５質量％以上２．０質量％以下の範囲内で含有してもよい。Ｂ２Ｏ３、Ｋ２Ｏ、Ｎａ２ＯおよびＰ２Ｏ５のガラス材料を１種以上、および／または、非晶質シリカを含有することで、これらガラス質添加物が骨材間において高温で軟化してスピネルの焼結を遅らせる。このため、ガラス材料や非晶質シリカを含有することで、不焼成れんが耐火物の耐スポール性の低下を抑制できる。 The unfired brick refractory according to the present embodiment further includes at least one kind of glass material of B 2 O 3 , K 2 O, Na 2 O and P 2 O 5 and / or 0 of amorphous silica. You may contain in the range of 0.5 mass% or more and 2.0 mass% or less. By containing one or more glass materials of B 2 O 3 , K 2 O, Na 2 O and P 2 O 5 and / or amorphous silica, these glassy additives can be heated at high temperatures between the aggregates. Softens to delay the spinel sintering. For this reason, the fall of the spall resistance of a non-fired brick refractory can be suppressed by containing glass material and amorphous silica.
なお、Ｂ２Ｏ３、Ｋ２Ｏ、Ｎａ２ＯおよびＰ２Ｏ５のガラス材料のうち１種類以上、および／または、非晶質シリカの含有量を０．５質量％より少なくすると、不焼成れんが耐火物の耐スポール性の低下を抑制する効果が小さくなる。また、Ｂ２Ｏ３、Ｋ２Ｏ、Ｎａ２ＯおよびＰ２Ｏ５のガラス材料のうち１種類以上、および／または、非晶質シリカの含有量を２．０質量％より多くすると、不焼成れんが耐火物が硬くなり、加熱によって割れてしまうので好ましくない。 In addition, when one or more kinds of glass materials of B 2 O 3 , K 2 O, Na 2 O and P 2 O 5 and / or the content of amorphous silica is less than 0.5% by mass, The effect of suppressing the decrease in the spall resistance of the fired brick is reduced. Further, if one or more of the glass materials of B 2 O 3 , K 2 O, Na 2 O and P 2 O 5 and / or the content of amorphous silica is more than 2.0% by mass, Baking bricks are not preferable because the refractory becomes hard and cracks by heating.
本実施形態に係る不焼成れんが耐火物を製造するには、高炉樋の使用済耐火物を１０質量％以上７０質量％以下の範囲内の割合で配合し、残部には、電融アルミナ、炭化ケイ素および鱗状黒鉛といったバージン原料を配合して耐火物原料を製造する。この耐火物原料にバインダーを外掛けで１質量％以上４質量％以下の範囲内で加えて混練し、プレス機を用いて成型する。成型された成型体を加熱処理することでバインダーを固化させるとともに成型体を乾燥させて不焼成れんが耐火物を製造する。 In order to produce the unfired brick refractory according to the present embodiment, the spent refractory of the blast furnace is blended at a ratio in the range of 10% by mass to 70% by mass, and the balance is fused alumina, carbonized. A refractory material is produced by blending virgin materials such as silicon and scaly graphite. A binder is added to the refractory raw material within a range of 1% by mass or more and 4% by mass or less, and the mixture is kneaded and molded using a press. The binder is solidified by heat-treating the molded body, and the molded body is dried to produce an unfired brick refractory.
バインダーには、レゾール型やノボラック型のフェノール樹脂が一般に用いられるが、糖蜜やデキストリンなどの有機系バインダーや、りん酸やけい酸ソーダなどの無機系バインダーを用いてもよい。また、プレス機には、真空フリクションプレスが一般に用いられるが、フリクションプレスやオイルプレス機を用いてもよい。成型力は、３００ｔ以上５０００ｔ以下の範囲内で、れんがの大きさに合わせて、適切なプレス機を選んでよい。 As the binder, a resol type or novolac type phenol resin is generally used, but an organic binder such as molasses or dextrin, or an inorganic binder such as phosphoric acid or sodium silicate may be used. In addition, a vacuum friction press is generally used as the press machine, but a friction press or an oil press machine may be used. An appropriate pressing machine may be selected in accordance with the size of the brick within a range of 300 to 5000 t.
このように、本実施形態に係る不焼成れんが耐火物は、Ａｌ２Ｏ３、ＳｉＣおよびＣを主成分とし、当該不焼成れんが耐火物の原料として高炉樋の使用済耐火物を１０質量％以上７０質量％以下の範囲内で含有する。これにより、耐食性を高めながら、耐スポール性の低下が抑制された不焼成れんが耐火物にできる。 Thus, the unfired brick refractory according to the present embodiment is mainly composed of Al 2 O 3 , SiC and C, and the refractory used as the raw material of the unfired brick is 10% by mass or more. It contains within the range of 70 mass% or less. Thereby, the non-fired brick in which the decrease in the spall resistance is suppressed while enhancing the corrosion resistance can be made into a refractory.
次に本発明の実施例について説明する。表１は、本実施例で用いた高炉樋の使用済耐火物の化学成分および鉱物成分を示す。本実施例では、高炉樋の使用済耐火物として、表１に示した使用済耐火物１と使用済耐火物２を用いた。 Next, examples of the present invention will be described. Table 1 shows the chemical components and mineral components of the used refractories of the blast furnace dredge used in this example. In this example, the used refractory 1 and the used refractory 2 shown in Table 1 were used as used refractories for the blast furnace.
表１に示した２種類の高炉樋の使用済耐火物を粒度が８ｍｍ以下になるまで粉砕して、不焼成れんが耐火物の原料とした。なお、本実施例においても、粒度が８ｍｍ以下とは、目開き８ｍｍの篩でふるい、篩下に篩分けされる粒度である。 The used refractories of the two types of blast furnaces shown in Table 1 were pulverized until the particle size became 8 mm or less, and used as raw materials for unfired brick refractories. In this example, the particle size of 8 mm or less is a particle size that is sieved with a sieve having an opening of 8 mm and sieved under the sieve.
表２は、実施例１〜１０の不焼成れんが耐火物の使用済耐火物の種類および含有量、添加物の種類および含有量、化学成分を示し、当該不焼成れんが耐火物のかさ密度、耐食性および耐スポール性をラボ評価した結果を示す。また、表３は、比較例１〜４の不焼成れんが耐火物の使用済耐火物の種類および含有量、添加物の種類および含有量、化学成分を示し、当該不焼成れんが耐火物のかさ密度、耐食性および耐スポール性をラボ評価した結果を示す。 Table 2 shows the types and contents of used refractories of the unfired brick refractories of Examples 1 to 10, the types and contents of additives, and chemical components, and the unfired brick refractory bulk density and corrosion resistance. The results of laboratory evaluation of the spall resistance are shown. Table 3 shows the types and contents of used refractories of the unfired brick refractories of Comparative Examples 1 to 4, the types and contents of additives, chemical components, and the unburned brick bulk density of the refractories. The results of laboratory evaluation of corrosion resistance and spall resistance are shown.
実施例１〜１０および比較例１〜４の不焼成れんが耐火物のいずれも、それぞれ表２および表３に示した化学成分となるように原料を配合した。すなわち、使用後の高炉樋耐火物を使用しないか、あるいは１０〜８０質量％の割合で配合し、残部に電融アルミナ、炭化ケイ素および鱗状黒鉛といったバージン原料を用いた。これらにバインダーとしてフェノール樹脂を用い、混練して得られた原料配合物を、フリクションプレス機を用いて１５０ＭＰａの圧力で成型し、２００℃で２４時間加熱処理してバインダーを固化させ、さらに、還元雰囲気下１４００℃で３ｈおよび還元雰囲気下１５００℃で２４時間焼成した。 The raw materials were blended so that each of the unfired brick refractories of Examples 1 to 10 and Comparative Examples 1 to 4 had the chemical components shown in Table 2 and Table 3, respectively. That is, the blast furnace refractory after use was not used, or was blended at a ratio of 10 to 80% by mass, and the remainder was made of virgin raw materials such as fused alumina, silicon carbide and scaly graphite. Using a phenol resin as a binder for these, the raw material composition obtained by kneading is molded at a pressure of 150 MPa using a friction press machine, heat-treated at 200 ° C. for 24 hours to solidify the binder, and further reduced. Firing was performed at 1400 ° C. for 3 hours in an atmosphere and at 1500 ° C. for 24 hours in a reducing atmosphere.
還元雰囲気下１４００℃で３ｈ焼成したサンプルを用いて耐食性評価を実施した。耐食性評価は、誘導炉内に当該耐火物を内張りし、温度１６００℃で塩基度１．４のスラグを用いて耐火物を侵食させて、侵食前後の耐火物の寸法差を溶損量とした。比較例１の寸法差を１００とし、実施例１〜１０および比較例２〜４の寸法差を比較例１の寸法差で規格化した耐食性指数で耐食性を評価した。なお、耐食性指数が小さいことは侵食前後の寸法差が少ないことになるので、その不焼成れんが耐火物は耐食性に優れることになる。 Corrosion resistance was evaluated using a sample fired at 1400 ° C. for 3 hours in a reducing atmosphere. In the corrosion resistance evaluation, the refractory is lined in an induction furnace, the refractory is eroded using a slag having a basicity of 1.4 at a temperature of 1600 ° C., and the dimensional difference between the refractories before and after the erosion is used as the amount of erosion. . The dimensional difference of Comparative Example 1 was set to 100, and the corrosion resistance was evaluated by the corrosion resistance index obtained by normalizing the dimensional differences of Examples 1 to 10 and Comparative Examples 2 to 4 with the dimensional difference of Comparative Example 1. In addition, since a small corrosion resistance index means a small dimensional difference before and after erosion, the unfired brick refractory is excellent in corrosion resistance.
一方、還元雰囲気下１５００℃で２４時間焼成したサンプルを用いて耐スポール性評価を実施した。耐スポール性評価は、１４００℃で１５分間加熱し、その後、１５分間の水冷を行うサイクルを５回繰り返し、試験開始前の動弾性率Ｅ０と、試験後の動弾性率Ｅ５の比Ｅ５／Ｅ０を算出した。比較例１のＥ５／Ｅ０を１００とし、実施例１〜１０および比較例２〜４のＥ５／Ｅ０の値を、比較例１のＥ５／Ｅ０の値で規格化した耐スポール性指数で耐スポール性を評価した。なお、比較例１は、スピネルを含有しないので、高い耐スポール性を示す。そのため、耐スポール性指数が大きいことは、比較例１に近い耐スポール性を有することを示し、当該不焼成れんが耐火物は耐スポール性に優れることになる。 On the other hand, the spall resistance was evaluated using a sample fired at 1500 ° C. for 24 hours in a reducing atmosphere. The evaluation of the spall resistance was performed by repeating the cycle of heating at 1400 ° C. for 15 minutes and then water-cooling for 15 minutes 5 times. Was calculated. The E5 / E0 of Comparative Example 1 is set to 100, and the values of E5 / E0 of Examples 1 to 10 and Comparative Examples 2 to 4 are normalized by the value of E5 / E0 of Comparative Example 1. Sex was evaluated. In addition, since the comparative example 1 does not contain spinel, it shows high spall resistance. Therefore, a large spall resistance index indicates that the spall resistance is similar to that of Comparative Example 1, and the unfired brick refractory is excellent in spall resistance.
比較例１および比較例２は、Ａｌ２Ｏ３、ＳｉＣおよびＣを含有する不焼成れんが耐火物であって、いずれも使用済耐火物を用いておらず、バージン原料を用いた不焼成れんが耐火物である。比較例１は、スピネルを含まない不焼成れんが耐火物であるので、耐食性は劣るが、耐スポール性に優れる不焼成れんが耐火物となった。一方、比較例２は、スピネルを３５．３質量％含有する不焼成れんが耐火物であるので、耐食性に優れるが、耐スポール性が劣る不焼成れんが耐火物となった。このため、耐食性については比較例１の値である１００を基準とし、耐スポール性については比較例２の値である５０を基準とした。 Comparative Example 1 and Comparative Example 2 are non-fired brick refractories containing Al 2 O 3 , SiC and C, both of which are not used refractories and are refractory bricks using virgin raw materials. It is a thing. In Comparative Example 1, unfired bricks that do not contain spinel are refractories, so the corrosion resistance is inferior, but unfired bricks that have excellent spall resistance are refractories. On the other hand, in Comparative Example 2, the unfired brick containing 35.3% by mass of spinel is a refractory, and thus the corrosion-resistant brick is inferior in spall resistance but is refractory. For this reason, the corrosion resistance was based on 100, which is the value of Comparative Example 1, and the spall resistance was based on 50, which is the value of Comparative Example 2.
実施例１〜３、実施例５〜７は、Ａｌ２Ｏ３、ＳｉＣおよびＣを含有する不焼成れんが耐火物であって、スピネル含有量が１１質量％の使用炭耐火物１またはスピネル含有量が６７質量％の使用済耐火物２を１０質量％以上５０質量％以下の範囲内で含有する不焼成れんが耐火物である。これらの不焼成れんが耐火物では、使用済耐火物１または使用済耐火物２の使用量を増やし、不焼成れんが耐火物のスピネル含有量が多くなるに従い耐食性が向上した。また、これらの不焼成れんが耐火物に含有されるスピネルは、焼結反応が進行したスピネルなので、焼結反応が進行していないスピネルを含有する比較例２よりも耐スポール性の低下が抑制された。 Examples 1 to 3 and Examples 5 to 7 are unfired brick refractories containing Al 2 O 3 , SiC and C, and used coal refractory 1 or spinel content having a spinel content of 11% by mass. Is a non-fired brick refractory containing 67% by mass of used refractory 2 in a range of 10% by mass to 50% by mass. In these unfired brick refractories, the amount of used refractory 1 or used refractory 2 was increased, and the corrosion resistance improved as the spinel content of the unfired brick refractory increased. Moreover, since the spinel contained in these refractory bricks is a spinel in which the sintering reaction has progressed, a decrease in the spall resistance is suppressed as compared with Comparative Example 2 containing spinel in which the sintering reaction has not progressed. It was.
実施例４および実施例８は、使用炭耐火物１または使用済耐火物２を７０質量％含有する不焼成れんが耐火物である。これらの不焼成れんが耐火物では、使用済耐火物に含まれるスピネルによって耐食性向上の効果が得られていないが、比較例２よりも耐スポール性の低下が抑制された。実施例４および実施例８の不焼成れんが耐火物は、使用炭耐火物１または使用炭耐火物２の含有量が７０質量％と多く、不焼成れんが耐火物のＳｉＣ含有量が多くなり、不焼成れんが耐火物に必要とされるＡｌ２Ｏ３およびスピネルが確保できなくなり、耐食性が比較例１と同じになった。 Example 4 and Example 8 are unfired brick refractories containing 70% by mass of the used charcoal refractory 1 or the used refractory 2. With these unfired brick refractories, the effect of improving corrosion resistance was not obtained by the spinel contained in the used refractories, but the decrease in spall resistance was suppressed as compared with Comparative Example 2. In the unfired brick refractory of Example 4 and Example 8, the content of the used coal refractory 1 or the used coal refractory 2 is as large as 70% by mass, and the unburned brick refractory has a high SiC content. Al 2 O 3 and spinel required for refractory fired bricks could not be secured, and the corrosion resistance was the same as in Comparative Example 1.
これらの結果から、使用済耐火物１または使用済耐火物２を１０質量％以上７０質量％以下の範囲内で含有させることで不焼成れんが耐火物の耐食性を比較例１と同等以上にでき、比較例２よりも耐スポール性の低下を抑制できることが確認された。 From these results, the corrosion resistance of the unfired brick refractory can be made equal to or higher than that of Comparative Example 1 by including the used refractory 1 or the used refractory 2 within the range of 10% by mass or more and 70% by mass or less. It was confirmed that the deterioration of the spall resistance can be suppressed as compared with Comparative Example 2.
実施例９は、Ａｌ２Ｏ３、ＳｉＣおよびＣを含有する不焼成れんが耐火物であって、スピネル含有量が６７質量％の使用済耐火物２を５０質量％含有し、さらに、ガラス材料としてＢ２Ｏ３を１．０質量％含有させた不焼成れんが耐火物である。このように、ガラス材料を含有させることによって、使用済耐火物２を５０質量％含有させている実施例７と比較して、さらに、不焼成れんが耐火物の耐スポール性を向上できることが確認された。 Example 9 is a non-fired brick refractory containing Al 2 O 3 , SiC and C, containing 50% by weight of used refractory 2 having a spinel content of 67% by weight, and further, as a glass material An unfired brick containing 1.0% by mass of B 2 O 3 is a refractory. Thus, it was confirmed that the inclusion of the glass material can further improve the spall resistance of the non-fired brick refractory compared to Example 7 containing 50% by mass of the used refractory 2. It was.
実施例１０は、Ａｌ２Ｏ３、ＳｉＣおよびＣを含有する不焼成れんが耐火物であって、スピネル含有量が６７質量％の使用済耐火物２を５０質量％含有し、さらに、非晶質シリカを１．０質量％含有させた不焼成れんが耐火物である。このように、非晶質シリカを含有させることによって、使用済耐火物２を５０質量％含有させている実施例７と比較して、さらに、不焼成れんが耐火物の耐スポール性を向上できることが確認された。 Example 10 is a non-fired brick refractory containing Al 2 O 3 , SiC and C, containing 50% by weight of used refractory 2 having a spinel content of 67% by weight, and amorphous. Unfired brick containing 1.0% by mass of silica is a refractory. Thus, by containing amorphous silica, compared with Example 7 containing 50% by mass of the used refractory 2, it is possible to further improve the spall resistance of the unfired brick refractory. confirmed.
比較例３は、Ａｌ２Ｏ３、ＳｉＣおよびＣを含有する不焼成れんが耐火物であって、スピネル含有量が１１質量％の使用済耐火物１を８０質量％含有させた不焼成れんが耐火物である。比較例３に示すように、使用済耐火物１の含有量を１０〜７０質量％の範囲外である８０質量％にすると、比較例２よりも耐スポール性の低下を抑制できるものの不焼成れんが耐火物の耐食性は比較例１よりも低化した。 Comparative Example 3 is an unfired brick refractory containing Al 2 O 3 , SiC, and C, and containing 80% by weight of a used refractory 1 having a spinel content of 11% by weight. It is. As shown in Comparative Example 3, when the content of the used refractory 1 is 80% by mass, which is outside the range of 10 to 70% by mass, the decrease in the spall resistance can be suppressed as compared with Comparative Example 2, but the non-fired bricks. The corrosion resistance of the refractory was lower than that of Comparative Example 1.
比較例４は、Ａｌ２Ｏ３、ＳｉＣおよびＣを含有する不焼成れんが耐火物であって、スピネル含有量が６７質量％の使用済耐火物２を８０質量％含有させた不焼成れんが耐火物である。比較例４に示すように使用済耐火物２の含有量を１０〜７０質量％の範囲外である８０質量％にすると、比較例２よりも耐スポール性の低下を抑制できるものの不焼成れんが耐火物の耐食性は比較例１よりも低化した。 Comparative Example 4 is an unfired brick refractory containing Al 2 O 3 , SiC and C, and containing 80% by weight of used refractory 2 having a spinel content of 67% by weight. It is. As shown in Comparative Example 4, when the content of the used refractory 2 is 80% by mass, which is outside the range of 10 to 70% by mass, a decrease in spall resistance can be suppressed as compared with Comparative Example 2, but unfired brick is refractory. The corrosion resistance of the product was lower than that of Comparative Example 1.
比較例３および比較例４の不焼成れんが耐火物は、使用炭耐火物１または使用炭耐火物２の含有量が８０質量％と多く、不焼成れんが耐火物のＳｉＣ含有量が多くなる。このため、不焼成れんが耐火物に必要とされるＡｌ２Ｏ３およびスピネルが確保できなくなり耐食性が低下した。 In the non-fired brick refractories of Comparative Example 3 and Comparative Example 4, the content of the used coal refractory 1 or the used coal refractory 2 is as large as 80% by mass, and the SiC content of the unfired brick refractory increases. For this reason, Al 2 O 3 and spinel required for non-fired bricks as refractories cannot be secured, resulting in a decrease in corrosion resistance.
このように、Ａｌ２Ｏ３、ＳｉＣおよびＣを含有する不焼成れんが耐火物であって、スピネルを含有する高炉樋の使用済耐火物を、１０質量％以上７０質量％以下の範囲内で含有させることによって、不焼成れんが耐火物の耐食性を向上させながら、耐スポール性の低下を抑制できることが確認された。また、さらに、Ｂ２Ｏ３、Ｋ２Ｏ、Ｎａ２ＯおよびＰ２Ｏ５のガラス材料のうち１種類以上、および／または、非晶質シリカを０．５質量％以上２．０質量％以下の範囲内で含有させることによって、不焼成れんが耐火物の耐スポール性を向上できることが確認された。 Thus, unfired bricks containing Al 2 O 3 , SiC and C are refractories, and contain spent refractories of blast furnaces containing spinel within a range of 10 mass% to 70 mass%. It was confirmed that the deterioration of the spall resistance can be suppressed while improving the corrosion resistance of the non-fired brick refractory. Further, one or more kinds of glass materials of B 2 O 3 , K 2 O, Na 2 O and P 2 O 5 and / or 0.5% by mass or more and 2.0% by mass of amorphous silica are used. It was confirmed that the non-fired brick can improve the spall resistance of the refractory by containing it within the following range.
このように、耐食性が向上された不焼成れんが耐火物を溶銑の予備処理が実施される溶銑搬送容器または溶銑鍋に用いることで、当該不焼成れんが耐火物の寿命を向上させることができ、これにより溶銑搬送容器および溶銑鍋の寿命をも向上させることができる。 Thus, by using the non-fired brick refractory with improved corrosion resistance in the hot metal transport container or hot metal pan in which the hot metal pretreatment is performed, the non-fired brick can improve the life of the refractory. Thus, the service life of the hot metal transport container and hot metal ladle can be improved.
１０ 高炉樋耐火物
１２ メタルライン材
１４ スラグライン材
１６ 溶銑
１８ 高炉スラグ
10 Blast furnace refractories 12 Metal line material 14 Slag line material 16 Hot metal 18 Blast furnace slag
Claims (5)
スピネルを含有する高炉樋の使用済耐火物を、１０質量％以上７０質量％以下の範囲内で含有する、不焼成れんが耐火物。 The unfired brick containing Al 2 O 3 , SiC and C is a refractory,
A non-fired brick refractory containing a spent refractory of a blast furnace containing spinel within a range of 10% by mass to 70% by mass.
スピネルを１０質量％以上７０質量％以下の範囲内で含有する高炉樋の使用済耐火物を１０質量％以上７０質量％以下の範囲内で含有し、
Ｂ２Ｏ３、Ｋ２Ｏ、Ｎａ２ＯおよびＰ２Ｏ５のガラス材料のうち１種類以上、および／または、非晶質シリカを０．５質量％以上２．０質量％以下の範囲内で含有する耐火物原料に、バインダーを外掛けで１質量％以上４質量％以下の範囲内で加えて混練し、成型した後に乾燥させる、不焼成れんが耐火物の製造方法。 A method for producing an unfired brick refractory containing Al 2 O 3 , SiC and C,
Containing a spent refractory of a blast furnace containing 10% by weight or more and 70% by weight or less of a blast furnace containing spinel within a range of 10% by weight or more and 70% by weight or less;
One or more kinds of glass materials of B 2 O 3 , K 2 O, Na 2 O and P 2 O 5 and / or amorphous silica in a range of 0.5 mass% to 2.0 mass% A method for producing a non-fired brick refractory, comprising adding a binder to the refractory raw material contained in 1 to 4% by weight in a range of 1% by mass or more, kneading, molding and drying.
０．３テスラ未満の磁束密度で磁力選別し、
さらに、０．３テスラ以上の磁束密度で磁力選別し、
さらに、密度分離して、前記高炉樋の使用済耐火物を製造する、請求項４に記載の不焼成れんが耐火物の製造方法。 Crushing the blast furnace slag containing the metal line material after use,
Magnetic separation with a magnetic flux density of less than 0.3 Tesla,
Furthermore, the magnetic force is selected with a magnetic flux density of 0.3 Tesla or more,
Furthermore, the density-separated and the used refractory of the said blast furnace firewood are manufactured, The manufacturing method of the unfired brick refractory of Claim 4.
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