JP2023094018A - Carbon-containing non-fired brick refractory and manufacturing method of carbon-containing non-fired brick refractory - Google Patents
Carbon-containing non-fired brick refractory and manufacturing method of carbon-containing non-fired brick refractory Download PDFInfo
- Publication number
- JP2023094018A JP2023094018A JP2021209212A JP2021209212A JP2023094018A JP 2023094018 A JP2023094018 A JP 2023094018A JP 2021209212 A JP2021209212 A JP 2021209212A JP 2021209212 A JP2021209212 A JP 2021209212A JP 2023094018 A JP2023094018 A JP 2023094018A
- Authority
- JP
- Japan
- Prior art keywords
- refractory
- carbon
- transition metal
- mass
- raw material
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000011451 fired brick Substances 0.000 title abstract 5
- 239000011230 binding agent Substances 0.000 claims abstract description 63
- 239000002994 raw material Substances 0.000 claims abstract description 43
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 31
- 150000003624 transition metals Chemical class 0.000 claims abstract description 31
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 19
- 239000010439 graphite Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000011368 organic material Substances 0.000 claims abstract description 3
- 239000011449 brick Substances 0.000 claims description 60
- 239000000126 substance Substances 0.000 claims description 20
- 239000011819 refractory material Substances 0.000 claims description 17
- 238000000465 moulding Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 239000011452 unfired brick Substances 0.000 claims description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 1
- 238000004901 spalling Methods 0.000 abstract description 14
- 238000009434 installation Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 19
- 239000000654 additive Substances 0.000 description 17
- 230000000996 additive effect Effects 0.000 description 14
- 239000005011 phenolic resin Substances 0.000 description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 13
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 229920001568 phenolic resin Polymers 0.000 description 12
- 239000002041 carbon nanotube Substances 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 239000002134 carbon nanofiber Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000035939 shock Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002923 metal particle Substances 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 5
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 229910003472 fullerene Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000009628 steelmaking Methods 0.000 description 3
- -1 transition metal salt Chemical class 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011302 mesophase pitch Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
Landscapes
- Furnace Housings, Linings, Walls, And Ceilings (AREA)
- Carbon Steel Or Casting Steel Manufacturing (AREA)
Abstract
Description
本発明は、製鉄用精錬設備等の高温プロセスで内張りとして用いられるカーボン含有不焼成れんが耐火物及びカーボン含有不焼成れんが耐火物の製造方法に関する。 TECHNICAL FIELD The present invention relates to a carbon-containing unburned brick refractory used as a lining in a high-temperature process such as an iron-making refining facility, and a method for producing the carbon-containing unburned brick refractory.
従来、カーボンを含有するれんが耐火物として代表的な耐火物には、例えばＭｇＯ－Ｃれんが、Ａｌ２Ｏ３－Ｃれんが、Ａｌ２Ｏ３－ＳｉＣ－Ｃれんが等がある。特にＭｇＯ－Ｃれんがは、製鋼スラグへの耐食性が良好であること、焼成れんがと比較して、比較的良好な耐熱衝撃性を備えること等の特徴を有し、製鋼工程の主要設備における内張り耐火物として主に使用されている。その一方、ＭｇＯ－Ｃれんがはカーボンを含有しているため、焼成れんがに比べて熱伝導率が高い。 Conventionally, representative refractories of carbon-containing brick refractories include, for example, MgO--C bricks, Al 2 O 3 --C bricks, and Al 2 O 3 --SiC--C bricks. In particular, MgO-C bricks are characterized by good corrosion resistance to steelmaking slag and relatively good thermal shock resistance compared to sintered bricks. Mainly used as a commodity. On the other hand, MgO--C bricks contain carbon, so they have higher thermal conductivity than baked bricks.
また、地球環境のため、世界的規模でのＣＯ２排出量の削減活動がなされている。製鉄業においても、多量の炭材を使用するため、高炉の還元材比の低減に伴う熱エネルギーの損失の抑制や、熱の有効利用化技術の開発など、ＣＯ２削減のための様々な取り組みが重要となっている。耐火物分野においては、熱余裕創出の策として、耐火物の低熱伝導化による炉体からの熱放散の抑止があげられる。特に、ＭｇＯ－Ｃれんが等のカーボン含有れんがは、熱伝導率にカーボン濃度依存性が見られるため、低カーボン化は熱エネルギーの損失の抑制に大きく寄与する。また、れんがの低カーボン化は、精錬時におけるカーボンピックアップの抑止など鋼片品質の向上にも寄与する。 Also, for the sake of the global environment, efforts are being made to reduce CO 2 emissions on a global scale. The steel industry also uses a large amount of carbonaceous material, so various efforts are being made to reduce CO2 emissions, such as controlling the loss of thermal energy due to the reduction of the reducing agent ratio in blast furnaces and developing technologies for effective utilization of heat. has become important. In the field of refractories, as a measure to create a thermal margin, it is possible to suppress heat dissipation from the furnace body by reducing the thermal conductivity of refractories. In particular, in carbon-containing bricks such as MgO--C bricks, since the thermal conductivity depends on the carbon concentration, the reduction in carbon content greatly contributes to the suppression of heat energy loss. In addition, reducing the carbon content of bricks contributes to improving billet quality, such as preventing carbon pick-up during refining.
ＭｇＯ－Ｃれんが等のカーボン含有れんが耐火物を低カーボン化した場合、課題となるのが耐熱スポーリング性の低下である。特に、製鉄プロセスで使用される耐火物（ＭｇＯ－Ｃれんが）のスポーリング破壊は、長期間による繰り返し熱負荷等で耐火物内に発生したクラックが進展することによって起こる。近年、その対策として、耐熱スポーリング性の低下を抑制したカーボンＭｇＯ－Ｃれんがが提案されている。例えば、特許文献１には、カーボン源としてカーボンファイバー（長さ０．１３～５０ｍｍ、径５μｍ以上）を５０％以下の範囲で耐火物中に添加する技術が開示されている。 When carbon-containing brick refractories such as MgO--C bricks are made to have a low carbon content, the problem is a decrease in heat spalling resistance. In particular, spalling failure of refractories (MgO--C bricks) used in the iron-making process occurs due to the development of cracks generated in the refractories due to repeated heat loads over a long period of time. In recent years, as a countermeasure, carbon MgO--C bricks have been proposed that suppress deterioration in heat spalling resistance. For example, Patent Document 1 discloses a technique of adding carbon fibers (0.13 to 50 mm in length, 5 μm or more in diameter) as a carbon source to a refractory in a range of 50% or less.
また、近年、カーボンブラックや、カーボンナノチューブ（以下、「ＣＮＴ」と記載することがある。）、カーボンナノファイバー（以下、「ＣＮＦ」と記載することがある。）、フラーレン、グラフェンなど、数多くのカーボンナノ材料が発見され、それらナノマテリアルの添加により機械特性向上、特に、耐スポーリング性の向上を図った技術も多く使用されている。例えば、特許文献２には、メゾフェーズピッチ＋熱硬化性樹脂を耐火物中に添加させて、メゾフェーズピッチ＋熱硬化性樹脂の熱分解（１０００℃以下）により、カーボンナノファイバー（径：最大５００ｎｍ、長さ：１００μｍ）を生成させ、耐食性かつ耐熱衝撃性を向上させる技術が開示されている。また、特許文献３には、フラーレン類を５％以下の範囲で耐火物中に添加し、耐スポーリング性の向上を図る技術が開示されている。その原理は、フラーレン類とバインダーであるフェノールレジンとが熱間（熱処理：最大１５００℃）で反応し、カーボンナノファイバー（ＣＮＦ）が生成することに因る。この生成されたＣＮＦが、ブリッジング効果の役割をなすため、耐スポーリング性の向上が達成される。ここで、耐スポーリング性の一種として、耐熱スポーリング性がある。 In recent years, carbon black, carbon nanotubes (hereinafter sometimes referred to as "CNT"), carbon nanofibers (hereinafter sometimes referred to as "CNF"), fullerenes, graphene, etc. Carbon nanomaterials have been discovered, and many techniques have been used to improve mechanical properties, particularly spalling resistance, by adding these nanomaterials. For example, in Patent Document 2, mesophase pitch + thermosetting resin is added to a refractory, and carbon nanofibers (diameter: maximum 500 nm, length: 100 μm) to improve corrosion resistance and thermal shock resistance. Further, Patent Document 3 discloses a technique of adding fullerenes in a range of 5% or less to a refractory to improve spalling resistance. The principle is that fullerenes and phenolic resin as a binder react in a hot state (heat treatment: maximum 1500° C.) to generate carbon nanofibers (CNF). Since this generated CNF plays a role of bridging effect, improvement of spalling resistance is achieved. Here, one type of spalling resistance is heat spalling resistance.
特許文献４には、有機バインダーと、粒径１０００ｎｍ以下の微粒子が溶媒中に分散されたコロイド状又は懸濁液状の遷移金属又は遷移金属塩の溶液又は分散液と、耐火物原料とを混練し、６００℃～１２００℃の温度で熱処理し、炭素繊維状組織と粒子径１０００ｎｍ以下の遷移金属又は遷移金属塩とを含む微粒子を分散して生成することにより、耐火物の靭性を向上させる技術が開示されている。 In Patent Document 4, an organic binder, a solution or dispersion of a colloidal or suspension-like transition metal or transition metal salt in which fine particles having a particle size of 1000 nm or less are dispersed in a solvent, and a refractory raw material are kneaded. , heat treatment at a temperature of 600 ° C. to 1200 ° C. to disperse and generate fine particles containing a carbon fibrous structure and a transition metal or transition metal salt with a particle size of 1000 nm or less, thereby improving the toughness of the refractory. disclosed.
また、特許文献５には、耐火原料の表面に触媒として、Ｖ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｏ、Ｐｄ、Ｒｈ、Ｗ、Ｐｔからなる群のうち１種または２種以上の金属が被覆された触媒被覆耐火原料と、有機高分子樹脂またはその前駆体とを原料とし、その耐火物を熱処理することによって、組織中にナノカーボンチューブを均一に分散させて、靭性を向上させる技術が開示されている。 Further, in Patent Document 5, one or more metals selected from the group consisting of V, Fe, Co, Ni, Cu, Mo, Pd, Rh, W, and Pt are coated on the surface of a refractory raw material as a catalyst. The catalyst-coated refractory raw material and the organic polymer resin or its precursor are used as raw materials, and the refractory is heat-treated to uniformly disperse the nanocarbon tubes in the structure and improve the toughness. It is
更に、特許文献６には、耐火物原料の表面にＣＮＴ、ＣＮＦを被覆した耐火原料を用いた耐火物を適用することにより、強度や耐破壊特性に優れた耐火物を提供する技術が開示されている。 Furthermore, Patent Document 6 discloses a technique for providing a refractory with excellent strength and fracture resistance by applying a refractory using a refractory raw material in which the surface of the refractory raw material is coated with CNT or CNF. ing.
これらの技術は、いずれも耐火物の組織中に繊維状物質を存在させて、繊維状物質によるブリッジング効果により、機械的負荷を原因とした耐火物中に発生する亀裂の進展を防ぐことを狙いとする。なお、上記した従来技術は、カーボン含有率の低い低カーボンれんがのみならず、比較的高いカーボン含有量を有するれんがにも適用でき、耐火物の更なる高強度化、あるいは耐スポーリング性の更なる向上に寄与している。 All of these techniques prevent the propagation of cracks that occur in the refractory due to mechanical loads by making fibrous substances exist in the structure of the refractory and by the bridging effect of the fibrous substances. aim. The above-described prior art can be applied not only to low-carbon bricks having a low carbon content but also to bricks having a relatively high carbon content, thereby further increasing the strength of refractories or improving spalling resistance. contributing to further improvement.
しかしながら、特許文献１のように繊維物質を添加する場合、耐火物の緻密性が損なわれ、逆に耐火物の成形が困難になるおそれがある。また、耐火物の製造コストの増大も招きかねない。特許文献２の場合には、添加する物質が比較的高価なメゾフェーズピッチであり、製造コストの面で問題がある。特許文献３の場合においても、添加する物質が比較的高価なフラーレンであり、耐火物の製造コストの増大も招きかねない。 However, when a fibrous material is added as in Patent Literature 1, the compactness of the refractory may be impaired and, conversely, molding of the refractory may become difficult. Moreover, the increase of the manufacturing cost of a refractory may be caused. In the case of Patent Document 2, the substance to be added is mesophase pitch, which is relatively expensive, and there is a problem in terms of manufacturing cost. In the case of Patent Document 3 as well, the substance to be added is fullerene, which is relatively expensive, which may lead to an increase in the manufacturing cost of the refractory.
また、特許文献４の場合、液状の有機バインダーとともにコロイド状、または液状の物質を新たに添加することになる。この時、混錬物の流動性が過剰に増大し、耐火物の成形が非常に困難になる。これは、バインダー添加量をコロイド状物質、あるいは懸濁液量の制限を結果として生じさせることになり、耐火物の製造に関して大きな制約を受けることになる。さらに、特許文献５及び特許文献６に開示された技術は、両者ともに被覆技術を適用したものである。この被覆技術は、通常ＣＶＤ等の蒸着法を用いるが、この手法もコストが非常に高くなり、また、大量に被覆することが非常に難しいのが課題である。したがって、これらの技術は必ずしも有効とは言えない。 Further, in the case of Patent Document 4, a colloidal or liquid substance is newly added together with the liquid organic binder. At this time, the fluidity of the kneaded material increases excessively, making molding of the refractory extremely difficult. As a result, the amount of binder to be added is limited to the amount of colloidal substance or suspension, which greatly restricts the production of refractories. Further, the techniques disclosed in Patent Documents 5 and 6 are both applied coating techniques. This coating technology usually uses a vapor deposition method such as CVD, but this method also has the problem that the cost is very high and it is very difficult to coat a large amount. Therefore, these techniques are not necessarily effective.
本発明は、かかる事情を鑑みてなされたもので、転炉への施工の後に当該転炉の予熱処理を経ることで、耐火物の耐熱スポーリング性を向上させることができるカーボン含有不焼成れんが耐火物及びカーボン含有不焼成れんが耐火物の製造方法を提供することを目的とする。 The present invention has been made in view of such circumstances, and carbon-containing unfired bricks that can improve the heat spalling resistance of refractories by undergoing preheating in the converter after construction in the converter. An object of the present invention is to provide a method for producing a refractory and a carbon-containing unburned brick refractory.
上記課題を解決する本発明の要旨構成は以下のとおりである。
［１］平均粒子径が１μｍ以下である遷移金属又は遷移金属を含有する遷移金属化合物を有機系物質からなる液状のバインダーに混合した混合物と、耐火物原料と、黒鉛原料と、を含有するカーボン含有不焼成れんが耐火物。
［２］前記耐火物原料は、Ａｌ２Ｏ３及びＭｇＯのうち少なくとも１種類の化合物で構成され、前記化合物は、平均粒子径で３ｍｍ以上が５～４０質量％、１ｍｍ以上３ｍｍ未満が１０～４５質量％、０．１５ｍｍ以上１ｍｍ未満が１５～３０質量％、及び０．１５ｍｍ未満が５～４５質量％の粒度範囲からなる、［１］に記載のカーボン含有不焼成れんが耐火物。
［３］前記バインダーの質量は、前記耐火物原料及び前記黒鉛原料の合計質量に対して外数で２質量％以上５質量％以下である、［１］又は［２］に記載のカーボン含有不焼成れんが耐火物。
［４］前記遷移金属化合物は、Ｆｅ又はＮｉを含有している化合物からなる、［１］～［３］のいずれか１つに記載のカーボン含有不焼成れんが耐火物。
［５］前記Ｆｅ又はＮｉを含有している化合物は、Ｆｅ２Ｏ３、Ｆｅ３Ｏ４、ＦｅＯ、ＮｉＣＯ３、及びＮｉＯのいずれかである、［４］に記載のカーボン含有不焼成れんが耐火物。
［６］前記遷移金属及び前記遷移金属化合物の合計質量は、前記バインダーの質量に対して０．１質量％以上８．０質量％以下である、［１］～［５］のいずれか１つに記載のカーボン含有不焼成れんが耐火物。
［７］平均粒子径が１μｍ以下である遷移金属又は遷移金属を含有する遷移金属化合物を有機系物質からなる液状のバインダーに混合して混合物を作成する混合工程と、前記混合工程で作成された前記混合物と、耐火物原料と、黒鉛原料と、を配合して成形する成形工程と、を有するカーボン含有不焼成れんが耐火物の製造方法。
The gist and configuration of the present invention for solving the above problems are as follows.
[1] Carbon containing a mixture obtained by mixing a transition metal having an average particle size of 1 μm or less or a transition metal compound containing a transition metal in a liquid binder made of an organic material, a refractory raw material, and a graphite raw material. Containing unfired brick refractories.
[2] The refractory raw material is composed of at least one compound selected from Al 2 O 3 and MgO. The carbon-containing unburned brick refractory according to [1], which has a particle size range of 45% by mass, 15 to 30% by mass for 0.15 mm or more and less than 1 mm, and 5 to 45% by mass for less than 0.15 mm.
[3] The carbon-free material according to [1] or [2], wherein the mass of the binder is 2% by mass or more and 5% by mass or less with respect to the total mass of the refractory raw material and the graphite raw material. Burnt brick refractories.
[4] The carbon-containing unburned brick refractory according to any one of [1] to [3], wherein the transition metal compound is a compound containing Fe or Ni.
[5] The carbon-containing unfired brick refractory according to [4], wherein the compound containing Fe or Ni is any one of Fe 2 O 3 , Fe 3 O 4 , FeO, NiCO 3 and NiO. thing.
[6] Any one of [1] to [5], wherein the total mass of the transition metal and the transition metal compound is 0.1% by mass or more and 8.0% by mass or less with respect to the mass of the binder The carbon-containing unburned brick refractory according to .
[7] A mixing step of mixing a transition metal having an average particle size of 1 μm or less or a transition metal compound containing a transition metal with a liquid binder made of an organic substance to prepare a mixture, and A method for producing a carbon-containing unburned brick refractory, comprising a molding step of blending and molding the mixture, a refractory raw material, and a graphite raw material.
本発明によれば、転炉への施工の後に当該転炉の予熱処理を経ることで、耐火物中に繊維状物質を効率的に生成させることが可能となる。そして、耐火物の耐熱スポーリング性の向上が可能となる。 According to the present invention, it is possible to efficiently generate a fibrous substance in a refractory by preheating the converter after applying it to the converter. Then, it becomes possible to improve the heat spalling resistance of the refractory.
以下、本発明の実施形態を通じて本発明を説明する。本発明における「不焼成れんが耐火物」は、耐火物原料、黒鉛原料、バインダー等を配合して成形する成形工程と、成形工程にて成形された成形物を焼成する焼成工程とを行うことによって製造されるれんが耐火物に対して、当該焼成工程を実施する前のれんが耐火物を意味する。なお、成形工程には、必要に応じてバインダーを熱硬化させるための処理（例えば成形品を１５０～３００℃程度で長時間（２４～７２時間）保持する処理（キュアリング処理））が含まれる。 Hereinafter, the present invention will be described through embodiments of the present invention. The "unfired brick refractory" in the present invention is obtained by performing a molding step of mixing and molding a refractory raw material, a graphite raw material, a binder, etc., and a firing step of firing the molded product formed in the molding step. It means the brick refractory before carrying out the firing process with respect to the brick refractory to be manufactured. In addition, the molding process includes a treatment for thermosetting the binder as necessary (for example, a treatment (curing treatment) in which the molded product is held at about 150 to 300 ° C. for a long time (24 to 72 hours)). .
製鋼プロセスにおいては、複数の精錬工程がバッチ式で実施されるため、熱の吸収及び放出が周期的に行われる。耐火物設備が繰り返しの熱負荷を受け続けると、耐火物に発生する熱応力もそれに応じて変動する。そのため耐火物内に亀裂が発生し、耐火物の破壊が引き起こされる。よって、耐火物の靭性を向上させて耐用性向上を達成できれば、製鉄プロセスにおける耐火物設備の寿命増加をもたらすことができる。 In the steelmaking process, multiple refining steps are carried out in batches, so that heat is absorbed and released cyclically. As the refractory equipment continues to be subjected to repeated thermal loads, the thermal stress generated in the refractory material fluctuates accordingly. This causes cracks in the refractory and causes destruction of the refractory. Therefore, if the toughness of the refractory can be improved and the durability can be improved, the service life of the refractory equipment in the steelmaking process can be increased.
耐火物の靭性を向上させる方法の一つとしては、材料内における破壊の原因となる亀裂の発生・進展を妨げることが挙げられる。亀裂の発生・進展を妨げる方法としては、繊維状物質のようなアスペクト比の高い物質を耐火物に添加し、ブリッジングを強化することが考えられる。ここで、繊維状物質としては、軽量で引張り強度の高い炭素繊維などが考えられる。しかし、単純に繊維状物質を添加すると、体積差や形状、表面状態などの点から、耐火物成形時にラミネーションが発生するなどの問題を有する。 One way to improve the toughness of a refractory is to prevent the initiation and propagation of cracks that cause fracture in the material. As a method of preventing the occurrence and propagation of cracks, it is conceivable to add a substance with a high aspect ratio such as a fibrous substance to the refractory to strengthen bridging. Here, as the fibrous substance, carbon fiber or the like which is lightweight and has high tensile strength can be considered. However, simply adding a fibrous material causes problems such as lamination during refractory molding due to differences in volume, shape, surface state, and the like.
ＭｇＯ－Ｃれんがなどに代表される耐火物は、骨材及び微粉などの耐火物原料、黒鉛原料（鱗状黒鉛）、フェノール樹脂などに代表される有機系物質からなる液状のバインダー、及びその他の各種添加材から構成される。その他の添加材としては、例えば硬化剤などが挙げられる。バインダーの種類によっては、硬化剤が必要な場合と不要な場合がある。 Refractories typified by MgO-C bricks are refractory raw materials such as aggregates and fine powders, graphite raw materials (flake graphite), liquid binders made of organic substances typified by phenol resins, and various other materials. Consists of additives. Other additives include, for example, curing agents. Depending on the type of binder, a curing agent may or may not be required.
ここで、有機系物質からなる液状のバインダーは、加熱すると揮発分が抜け、アモルファスカーボンなどの炭素物質が生成する。この時、バインダーを原料として、カーボンナノチューブなどのナノ繊維状物質を加熱中に生成させることができれば、より低コストでかつラミネーション発生などの課題を解決できる可能性がある。そこで、発明者らはバインダー材料（例えばタールや、フェノール樹脂、ピッチ等の有機樹脂）の加熱時にカーボンナノ繊維物質の生成可否について検討を行った。 Here, when a liquid binder made of an organic substance is heated, volatile matter is removed and a carbon substance such as amorphous carbon is generated. At this time, if nanofibrous substances such as carbon nanotubes can be generated during heating using a binder as a raw material, it may be possible to solve problems such as the occurrence of lamination at a lower cost. Therefore, the inventors investigated whether or not a carbon nanofiber substance can be generated when a binder material (for example, tar, phenolic resin, or organic resin such as pitch) is heated.
ここで、カーボンナノチューブの生成については、ＦｅやＮｉなどの遷移金属の微粒子が存在すると、その微粒子を核としてナノチューブが生成し成長する。そこで、発明者らは、加熱中にバインダー材料の成分により還元生成したＦｅやＮｉ粒子を核としたナノチューブ生成を狙いとして、ＦｅやＮｉの酸化物をバインダー材料に添加して観察を行った。以下、調査実験内容を記す。 Here, regarding the generation of carbon nanotubes, if fine particles of a transition metal such as Fe or Ni are present, nanotubes are generated and grow using the fine particles as nuclei. Therefore, the inventors added oxides of Fe and Ni to the binder material and observed them, with the aim of generating nanotubes with cores of Fe and Ni particles reduced by the components of the binder material during heating. The contents of the research experiment are described below.
原料は、遷移金属化合物として粉末状のＦｅ２Ｏ３又はＮｉＣＯ３を用い、バインダーとしてフェノール樹脂を用いた。カーボンるつぼの中にフェノール樹脂を１０ｇ添加し、その後、粉末状のＦｅ２Ｏ３、もしくはＮｉＣＯ３をるつぼ内に添加した。添加量、および実験水準を表１に示す。それぞれの条件とも、るつぼ内でフェノール樹脂と粉末状の遷移金属化合物とを十分に混合し、図１に示す温度パターンにて、Ａｒ雰囲気で加熱した。冷却後の試料をＴＥＭ（透過電子顕微鏡）にて観察した。それぞれの条件でのＴＥＭ写真を図２～３に示す。図２～３よりサブμｍサイズの擬繊維状のフェノール樹脂乾留生成物の存在が確認された。図２は、遷移金属化合物としてＦｅ２Ｏ３を用いた場合におけるフェノール樹脂乾留生成物の一例であるＣＮＴのＴＥＭ写真を示す。図３は、遷移金属化合物としてＮｉＣＯ３を用いた場合におけるフェノール樹脂乾留生成物の一例であるＣＮＴのＴＥＭ写真を示す。 Powdered Fe 2 O 3 or NiCO 3 was used as the transition metal compound, and phenol resin was used as the binder. 10 g of phenolic resin was added into a carbon crucible, and then powdered Fe 2 O 3 or NiCO 3 was added into the crucible. Table 1 shows the amounts added and the experimental levels. For each condition, the phenolic resin and the powdery transition metal compound were sufficiently mixed in a crucible and heated in an Ar atmosphere according to the temperature pattern shown in FIG. The sample after cooling was observed with a TEM (transmission electron microscope). TEM photographs under each condition are shown in FIGS. From FIGS. 2 and 3, the presence of pseudo-fibrous phenolic resin dry distillation products of sub-μm size was confirmed. FIG. 2 shows a TEM photograph of CNT, which is an example of a phenolic resin dry-distillation product when Fe 2 O 3 is used as a transition metal compound. FIG. 3 shows a TEM photograph of CNT, which is an example of a phenolic resin dry distillation product when NiCO 3 is used as a transition metal compound.
この調査実験結果を受け、粉末状のＮｉＣＯ３をバインダーに対して１質量％分添加して、バインダーと粉末状のＮｉＣＯ３を事前混合した混合物を作成し、当該混合物と、耐火物原料と、黒鉛原料とを配合して成形した成形物に対して加熱処理を行うことで、ＭｇＯ－１０％Ｃれんがを試作した。ここで、「ＭｇＯ－１０％Ｃれんが」は、マグネシア（ＭｇＯ）と、１０質量％の黒鉛原料（Ｃ）とを混合して成るれんがを意味する。れんがの曲げ強度（σ：ＭＰａ）、静的弾性率（Ｅ：ＭＰａ）を３点曲げ試験（ＪＩＳ Ｒ２２１３：２００５ 耐火れんがの曲げ強さの試験方法）から評価した。ここで、静的弾性率（Ｅ）は以下の（１）式を用いて評価した。ここで、Ｌは支点間距離（ｍ）、Ｂは試料の幅（ｍ）、Ｗは試料の高さ（ｍ）、Δｕはたわみ（ｍｍ）、ΔＰは線形域の最大荷重（Ｎ）である。 In response to the results of this research experiment, 1% by mass of powdered NiCO 3 was added to the binder to create a mixture in which the binder and powdered NiCO 3 were premixed, and the mixture, the refractory raw material, An MgO-10% C brick was experimentally manufactured by heat-treating a molded article formed by blending graphite raw material. Here, "MgO-10% C brick" means a brick obtained by mixing magnesia (MgO) and 10% by mass of graphite raw material (C). The bending strength (σ: MPa) and static elastic modulus (E: MPa) of the brick were evaluated from a three-point bending test (JIS R2213:2005 test method for bending strength of refractory bricks). Here, the static elastic modulus (E) was evaluated using the following formula (1). Here, L is the distance between fulcrums (m), B is the width of the sample (m), W is the height of the sample (m), Δu is the deflection (mm), and ΔP is the maximum load in the linear region (N). .
結果を図４～５に示す。図４は、縦軸を荷重（Ｎ）、横軸を変位（ｍｍ）として、変位と荷重との関係を示す図である。図５は、縦軸を静的弾性率（ＭＰａ）として示す図である。図４から曲げ強度の結果が分かり、図５から静的弾性率の結果が分かる。図５から、ＮｉＣＯ３を添加したＭｇＯ－１０％Ｃれんが（ＮｉＣＯ３添加れんが）の静的弾性率は、ＮｉＣＯ３を添加しなかった通常のＭｇＯ－Ｃれんが（通常れんが）の場合と比較してほぼ同様であることが確認できる。また、図４から、ＮｉＣＯ３添加れんがは、通常れんがと比較して曲げ強度が向上することも確認できる。これにより、次の（２）式で定義される熱衝撃破壊抵抗Ｒ（単位：Ｋ）は、ナノＮｉＣＯ３を添加したバインダーの適用によって向上することが示唆される。 The results are shown in Figures 4-5. FIG. 4 is a diagram showing the relationship between displacement and load, with the vertical axis representing load (N) and the horizontal axis representing displacement (mm). FIG. 5 is a diagram showing the vertical axis as static elastic modulus (MPa). FIG. 4 gives the flexural strength results and FIG. 5 gives the static modulus results. From FIG. 5, the static elastic modulus of the MgO-10%C brick with NiCO 3 added (NiCO 3 added brick) is higher than that of the normal MgO-C brick without NiCO 3 added (normal brick). It can be confirmed that the In addition, it can be confirmed from FIG. 4 that the NiCO 3 -added brick has improved bending strength compared to the ordinary brick. This suggests that the thermal shock fracture resistance R (unit: K) defined by the following equation (2) is improved by applying a binder to which nano-NiCO 3 is added.
（２）式において、νはポアソン比（無次元数（ここでは０．３））、αは材料の熱膨張係数（１／Ｋ）である。実際に熱衝撃破壊抵抗Ｒを両者で比較すると、通常れんがではＲが２２、ＮｉＣＯ３添加れんがではＲが３４となり、熱衝撃破壊抵抗Ｒが大きく増加した。 In the equation (2), ν is Poisson's ratio (a dimensionless number (here, 0.3)), and α is the thermal expansion coefficient (1/K) of the material. When the thermal impact fracture resistance R was actually compared between the two, the normal brick had an R of 22 and the NiCO 3 added brick had an R of 34, showing a large increase in the thermal impact fracture resistance.
ここで、本発明のＣＮＴ生成メカニズムについて、遷移金属としてＦｅＯを添加した場合を例に、図６を用いて説明する。熱処理の実施により、まず、図６（ａ）に示す通り、フェノール樹脂（レジン）から還元性ガス（ＣｘＨｙ、Ｈ２、ＣＯ）が揮発する。そして、図６（ｂ）に示す通り、還元性ガスとＦｅＯとが酸化還元反応を起こし、金属Ｆｅが生成する。その後、図６（ｃ）に示す通り、フェノール樹脂から揮発した還元性ガスが金属Ｆｅの表面で分解し、金属Ｆｅを核としてカーボンが生成及び拡散される。これを受けて、図６（ｄ）に示す通り、金属Ｆｅの触媒作用により、金属Ｆｅの表面において拡散されたカーボンが結合（Ｃ－Ｃ結合）し、ＣＮＴとして生成及び成長する。 Here, the CNT generation mechanism of the present invention will be described with reference to FIG. 6, taking as an example the case where FeO is added as a transition metal. By performing the heat treatment, first, reducing gases (CxHy, H 2 , CO) are volatilized from the phenolic resin (resin) as shown in FIG. 6(a). Then, as shown in FIG. 6(b), the reducing gas and FeO undergo an oxidation-reduction reaction to produce metallic Fe. After that, as shown in FIG. 6(c), the reducing gas volatilized from the phenolic resin is decomposed on the surface of the metal Fe, and carbon is generated and diffused with the metal Fe as the nucleus. In response to this, as shown in FIG. 6(d), the carbon diffused on the surface of the metal Fe bonds (CC bonds) due to the catalytic action of the metal Fe, and CNTs are generated and grown.
この熱処理中の反応を利用して、耐火物中に効率よくＣＮＴを生成、成長させることが可能である。転炉の築炉～操業を例にとると、築炉時はＣＮＴ生成前の耐火物を従来の耐火物と同様に施工し、転炉の予熱中（８００～１２００℃）に、図６に示す原理によって反応が起こり、ＣＮＴが耐火物内部に一様に生成される。この生成したＣＮＴによるブリッジング効果によって、耐火物の靭性が大きく向上して耐火物寿命向上が達成される。 Utilizing this reaction during heat treatment, it is possible to efficiently generate and grow CNTs in the refractory. Taking the construction and operation of a converter as an example, at the time of furnace construction, the refractory before CNT generation is constructed in the same way as the conventional refractory. A reaction takes place according to the principle shown, and CNTs are uniformly produced inside the refractory. Due to the bridging effect of the produced CNTs, the toughness of the refractory is greatly improved, and the service life of the refractory is improved.
ここで、本発明で用いるバインダーへの添加物（触媒）には、平均粒子径が１μｍ以下である遷移金属あるいは遷移金属を含有する遷移金属化合物（酸化物、炭酸塩その他化合物）を用いる必要がある。バインダーに添加する遷移金属（遷移金属化合物）の粒子が平均１μｍを超える場合、ＣＮＴが生成し難いためである。添加する粒子は遷移金属粒子を用いるのが最も好ましいが、比較的高価であると共に、取り扱い時の安全性に十分注意を払う必要がある。そこで、取扱い時の安全性を確保でき、同等の効果を有する意味で遷移金属化合物（酸化物や炭酸塩その他化合物）を添加するほうが望ましい。用いる遷移金属化合物としてはＦｅ、Ｎｉを含有する化合物であることが好ましく、さらにＮｉＣＯ３、Ｆｅ２Ｏ３、Ｆｅ３Ｏ４、ＦｅＯ、ＮｉＯ等であればなお好ましい。また、遷移金属として用いる場合は、Ｆｅ又はＮｉが好ましい。そして、バインダーへの添加物としては、遷移金属と遷移金属化合物との混合物（例えば、ＦｅとＦｅＯとの混合物）であってもよく、遷移金属化合物同士の混合物（例えば、Ｆｅ３Ｏ４とＦｅＯとの混合物）であってもよい。 Here, as the additive (catalyst) to the binder used in the present invention, it is necessary to use a transition metal having an average particle size of 1 μm or less or a transition metal compound containing a transition metal (oxide, carbonate or other compound). be. This is because CNTs are difficult to generate when the average particle size of the transition metal (transition metal compound) added to the binder exceeds 1 μm. Although it is most preferable to use transition metal particles as the particles to be added, they are relatively expensive and require careful attention to safety during handling. Therefore, it is desirable to add transition metal compounds (oxides, carbonates, and other compounds) in the sense that safety during handling can be ensured and equivalent effects can be obtained. The transition metal compound to be used is preferably a compound containing Fe or Ni, and more preferably NiCO 3 , Fe 2 O 3 , Fe 3 O 4 , FeO, NiO, or the like. Moreover, when using as a transition metal, Fe or Ni is preferable. The additive to the binder may be a mixture of a transition metal and a transition metal compound (for example, a mixture of Fe and FeO), or a mixture of transition metal compounds (for example, Fe 3 O 4 and FeO a mixture with).
ここで、本発明では、平均粒子径が１μｍ以下である遷移金属又は遷移金属化合物を予め有機系物質からなる液状のバインダーと混合して混合物にした後で、耐火物原料や黒鉛原料に添加して、カーボン含有不焼成れんが耐火物とすることを特徴とする。通常、耐火物に金属粒子を含有させる場合には、耐火物原料に金属粒子を添加することが一般的である。しかし、耐火物原料に金属粒子を添加した場合には、バインダーと金属粒子とが上手く混合されず、ＣＮＴの生成及び成長は難しい。また、特許文献４のように、溶液を介して金属粒子をバインダーに混合する場合には、耐火物の成形性が低下する。これに対し、本発明のように、耐火物原料及び黒鉛原料と配合して成形する工程（成形工程）の前に、遷移金属又は遷移金属化合物とバインダーとを予め混合させて混合物を作成する工程（混合工程）を設けることで、耐火物の成形性を低下させることなく遷移金属をバインダーに確実かつ均一に分散させることができ、ＣＮＴをより容易に生成、成長できる。なお、遷移金属（遷移金属化合物）とバインダーの混合方法は、ミキサーなどの撹拌機や混錬機など、様々な方法で行えばよく、その方法については限定しない。 Here, in the present invention, a transition metal or a transition metal compound having an average particle size of 1 μm or less is mixed in advance with a liquid binder made of an organic substance to form a mixture, and then added to a refractory raw material or a graphite raw material. and a carbon-containing unburned brick refractory. Usually, when metal particles are contained in the refractory, the metal particles are generally added to the refractory raw material. However, when metal particles are added to the refractory raw material, the binder and metal particles are not well mixed, making it difficult to generate and grow CNTs. In addition, as in Patent Document 4, when metal particles are mixed with a binder through a solution, the formability of the refractory deteriorates. In contrast, as in the present invention, a step of pre-mixing a transition metal or a transition metal compound with a binder to form a mixture prior to the step of blending with the refractory raw material and the graphite raw material and molding (forming step). By providing the (mixing step), the transition metal can be reliably and uniformly dispersed in the binder without deteriorating the formability of the refractory, and CNTs can be generated and grown more easily. Incidentally, the method of mixing the transition metal (transition metal compound) and the binder may be performed by various methods such as a stirrer such as a mixer or a kneader, and the method is not limited.
また、耐火物に添加するバインダーの質量は、耐火物原料及び黒鉛原料の合計質量に対して外数（外掛け）で２質量％以上５質量％以下とすることが望ましい。２質量％未満ではバインダーとして十分でなく、５質量％超えでは逆にバインダーが多すぎて耐火物の成形時にバインダーが染み出すおそれがある。 Further, the mass of the binder added to the refractory is desirably 2 mass % or more and 5 mass % or less with respect to the total mass of the refractory raw material and the graphite raw material. If it is less than 2% by mass, it is not sufficient as a binder.
さらに、平均粒子径が１μｍ以下である遷移金属（遷移金属化合物）の添加量は、有機系物質からなる液状のバインダーに対して、０．１質量％以上８．０質量％以下とすることが望ましい。０．１質量％未満ではＣＮＴ生成量が抑制され、８．０質量％よりも多い添加量では、８．０質量％と効果が同等であり過度の効果が望めない。また、逆に耐火物組織の細密充填性に影響を及ぼすため好ましくない。 Furthermore, the addition amount of the transition metal (transition metal compound) having an average particle size of 1 μm or less can be 0.1% by mass or more and 8.0% by mass or less with respect to the liquid binder made of an organic substance. desirable. If the content is less than 0.1% by mass, the amount of CNT produced is suppressed, and if the addition amount is more than 8.0% by mass, the effect is equivalent to that of 8.0% by mass, and an excessive effect cannot be expected. Moreover, it is not preferable because it adversely affects the close packing property of the refractory structure.
本発明は、ＭｇＯ－ＣやＡｌ２Ｏ３－Ｃなどの各種カーボン含有れんがに適用できる。なお、耐火物原料としてＡｌ２Ｏ３及びＭｇＯのうち少なくとも１種類の化合物を用いる場合、Ａｌ２Ｏ３及びＭｇＯの粒度範囲は、平均粒子径で３ｍｍ以上が５～４０質量％、１ｍｍ以上３ｍｍ未満が１０～４５質量％、０．１５ｍｍ以上１ｍｍ未満が１５～３０質量％、及び０．１５ｍｍ未満が５～４５質量％の粒度範囲とすることが耐火物として好ましい。もちろん、これらの耐火物にＡｌやＳｉなどの酸化防止剤を添加しても全くかまわない。むしろ、Ａｌなどがウィスカー生成に寄与するため、より高い効果が十分期待できる。また、ＳｉＣを添加した系の耐火物でも適用できる。 The present invention can be applied to various carbon-containing bricks such as MgO--C and Al.sub.2O.sub.3 -- C. When at least one compound of Al 2 O 3 and MgO is used as the refractory raw material, the particle size range of Al 2 O 3 and MgO is 5 to 40% by mass when the average particle size is 3 mm or more, and 1 mm or more and 3 mm. 10 to 45% by mass of less than 1 mm, 15 to 30% by mass of less than 0.15 mm to less than 1 mm, and 5 to 45% by mass of less than 0.15 mm. Of course, an antioxidant such as Al or Si may be added to these refractories. Rather, since Al and the like contribute to the formation of whiskers, a higher effect can be fully expected. Also, a refractory of a system to which SiC is added can be applied.
なお、本発明に使用する耐火物原料としては、電融品、焼結品、天然材質（海水ＭｇＯも含む）のいずれでも適用できる。また、黒鉛原料も、鱗状黒鉛、カーボンブラック、薄肉黒鉛など、各種材質が適用できる。 As the refractory raw material used in the present invention, any of electrofused products, sintered products, and natural materials (including seawater MgO) can be applied. Various materials such as flake graphite, carbon black, and thin graphite can be used as the graphite raw material.
最大サイズを５．００ｍｍとする電融ＭｇＯ骨材、１．００ｍｍ未満のＭｇＯ微粉、および鱗状黒鉛を用いてＭｇＯ－Ｃれんがを製造した。れんが中のカーボン濃度は１０．０質量％とした。基準となるＭｇＯ－Ｃれんがの組成を表２に示す。表２に示す組成のＭｇＯ－Ｃれんがは、以下に説明する表３及び表４において、比較例１として示す例である。 Electrofused MgO aggregate with a maximum size of 5.00 mm, MgO fines less than 1.00 mm, and flake graphite were used to produce MgO—C bricks. The carbon concentration in the brick was set to 10.0% by mass. Table 2 shows the composition of the standard MgO--C bricks. The MgO—C brick having the composition shown in Table 2 is an example shown as Comparative Example 1 in Tables 3 and 4 described below.
発明例、および比較例の一覧を表３に示す。発明例１は平均粒子径が１μｍ以下の添加物としてＣｏＣＯ３をバインダーに対して９．０質量％の割合でバインダーに予め混合して添加した。発明例２は平均粒子径が１μｍ以下の添加物としてＮｉＯをバインダーに対して８．０質量％の割合でバインダーに予め混合して添加した。発明例３は平均粒子径が１μｍ以下の添加物としてＦｅ３Ｏ４をバインダーに対して４．０質量％の割合でバインダーに予め混合して添加した。発明例４は平均粒子径が１μｍ以下の添加物としてＦｅＯをバインダーに対して８．０質量％の割合でバインダーに予め混合して添加した。発明例５は平均粒子径が１μｍ以下の添加物としてＦｅ２Ｏ３をバインダーに対して４．０質量％の割合でバインダーに予め混合して添加した。発明例６は平均粒子径が１μｍ以下の添加物として金属Ｆｅをバインダーに対して４．０質量％の割合でバインダーに予め混合して添加した。発明例７は平均粒子径が１μｍ以下の添加物としてＮｉをバインダーに対して４．０質量％の割合でバインダーに予め混合して添加した。発明例８は平均粒子径が１μｍ以下の添加物としてＣｏをバインダーに対して４．０質量％の割合でバインダーに予め混合して添加した。 Table 3 shows a list of invention examples and comparative examples. In Inventive Example 1, CoCO 3 as an additive having an average particle size of 1 μm or less was added to the binder at a rate of 9.0% by mass, which was previously mixed with the binder. In Inventive Example 2, NiO, as an additive having an average particle size of 1 μm or less, was added to the binder at a rate of 8.0% by mass, which was previously mixed with the binder. In Inventive Example 3, Fe 3 O 4 as an additive having an average particle size of 1 μm or less was added to the binder at a rate of 4.0% by mass with respect to the binder in advance. In Inventive Example 4, as an additive having an average particle size of 1 μm or less, FeO was added to the binder at a rate of 8.0% by mass, which was previously mixed with the binder. In Inventive Example 5, Fe 2 O 3 as an additive having an average particle size of 1 μm or less was added to the binder at a rate of 4.0% by mass, which was previously mixed with the binder. In Inventive Example 6, metal Fe was added as an additive having an average particle size of 1 μm or less by being premixed with the binder at a ratio of 4.0% by mass with respect to the binder. In Inventive Example 7, as an additive having an average particle size of 1 μm or less, Ni was added to the binder at a rate of 4.0% by mass, which was previously mixed with the binder. In Invention Example 8, as an additive having an average particle size of 1 μm or less, Co was added to the binder at a rate of 4.0% by mass, which was previously mixed with the binder.
これに対し、比較例１では表２に示す配合の通りで混合し、添加物には何も添加しなかった。比較例２もまた、表２に示す配合の通りで混合したが、添加物にＡｌ粉末を４．０質量％の割合でバインダーとは別に添加した。比較例３では表２に示す配合の通りで混合し、添加物にＳｉ粉末を４．０質量％の割合でバインダーに予め混合して添加した。比較例４は平均粒子径が１μｍ以下の添加物としてＮｉＣＯ３をバインダーに対して１０．０質量％の割合でバインダーとは別に添加した。比較例５は平均粒子径が１μｍ以下の添加物としてＦｅ２Ｏ３を８．５質量％の割合でバインダーとは別に添加した。ここで、比較例２、４、５における「バインダーと別々に添加」とは、金属粒子を耐火物原料に直接添加することを意味する。 On the other hand, in Comparative Example 1, the formulations shown in Table 2 were mixed, and no additives were added. Comparative Example 2 was also mixed according to the formulation shown in Table 2, but Al powder was added to the additive at a rate of 4.0% by mass separately from the binder. In Comparative Example 3, the mixture was mixed according to the composition shown in Table 2, and Si powder was added as an additive in advance by mixing with the binder at a ratio of 4.0% by mass. In Comparative Example 4, NiCO 3 as an additive having an average particle size of 1 μm or less was added separately from the binder at a rate of 10.0% by mass based on the binder. In Comparative Example 5, 8.5% by mass of Fe 2 O 3 was added separately from the binder as an additive having an average particle size of 1 μm or less. Here, "added separately from the binder" in Comparative Examples 2, 4, and 5 means that the metal particles are directly added to the refractory raw material.
発明例、比較例ともに原料の混練を行い、その後にフリクションプレス機を用いて成形を行なった。成形品を２３０℃で２４時間保持して、キュアリングを行なった後に、還元雰囲気中１３５０℃で３時間保持して、焼成処理を行い、評価用試料を得た。評価は、機械的特性として、曲げ強度σ（ＭＰａ）および弾性率（動的弾性率）Ｅ（ＭＰａ）を測定し、熱衝撃破壊抵抗Ｒを（２）式に従って導出した。この熱衝撃破壊抵抗Ｒが高いほど破壊しにくい材料となり、耐熱スポーリング性に優れる材料といえる。 In both invention examples and comparative examples, raw materials were kneaded and then molded using a friction press. The molded product was held at 230° C. for 24 hours for curing, and then held at 1350° C. for 3 hours in a reducing atmosphere for firing treatment to obtain an evaluation sample. For evaluation, bending strength σ (MPa) and elastic modulus (dynamic elastic modulus) E (MPa) were measured as mechanical properties, and thermal impact fracture resistance R was derived according to the formula (2). The higher the thermal impact fracture resistance R, the more difficult the material is to fracture, and it can be said that the material is excellent in heat spalling resistance.
結果を表４に示す。平均粒子径が１μｍ以下である遷移金属又は遷移金属化合物をバインダーに予め混合して添加した発明例１～８は、比較例１に比べて曲げ強度、弾性率が増加した。発明例１～８は、比較例１～３に比べて、熱衝撃破壊抵抗Ｒが向上した。発明例１～８は、比較例４、５よりも熱衝撃破壊抵抗Ｒが高く、靭性が向上した。更に、平均粒子径が１μｍ以下である遷移金属化合物としてＦｅ２Ｏ３を採択し、その添加量を４．０質量％として添加した発明例５は、８．０質量％超えで添加した比較例５に比べて熱衝撃破壊抵抗Ｒが向上した。なお、同一の添加方法（有機バインダーを予め混合して添加した条件）で平均粒子径が１μｍ以下である遷移金属又は遷移金属化合物の種類別に熱衝撃破壊抵抗Ｒを比較すると、発明例１～８では大きな差は見られなかった。 Table 4 shows the results. Inventive Examples 1 to 8, in which a transition metal or transition metal compound having an average particle size of 1 μm or less was previously mixed with a binder and added thereto, compared with Comparative Example 1, the flexural strength and elastic modulus increased. Inventive Examples 1-8 have improved thermal shock fracture resistance R compared to Comparative Examples 1-3. Inventive Examples 1 to 8 had higher thermal shock fracture resistance R and improved toughness than Comparative Examples 4 and 5. Furthermore, in Invention Example 5, Fe 2 O 3 was adopted as a transition metal compound having an average particle size of 1 μm or less, and the amount added was 4.0% by mass. Compared to 5, the thermal shock fracture resistance R was improved. When the thermal shock fracture resistance R is compared for each type of transition metal or transition metal compound having an average particle size of 1 μm or less under the same addition method (conditions in which an organic binder is added in advance), invention examples 1 to 8 are found. No big difference was found.
以上から、本発明に係るカーボン含有不焼成れんが耐火物及びカーボン含有不焼成れんが耐火物の製造方法を利用してカーボン含有不焼成れんが耐火物を製造し、転炉への施工の後に当該転炉の予熱処理を経ることで、耐火物中に繊維状物質を効率的に生成させることが可能となる。そして、カーボン含有れんが耐火物の熱衝撃破壊抵抗性、すなわち耐熱スポーリング性に対して優れた効果を有することが明らかとなった。 As described above, a carbon-containing unburned brick refractory and a method for producing a carbon-containing unburned brick refractory according to the present invention are used to manufacture a carbon-containing unburned brick refractory, and after installation in a converter, the converter is Through the preheat treatment, it becomes possible to efficiently generate fibrous substances in the refractory. It was also found that the carbon-containing brick refractory has an excellent effect on the thermal shock fracture resistance, that is, the heat spalling resistance.
Claims (7)
前記化合物は、平均粒子径で３ｍｍ以上が５～４０質量％、１ｍｍ以上３ｍｍ未満が１０～４５質量％、０．１５ｍｍ以上１ｍｍ未満が１５～３０質量％、及び０．１５ｍｍ未満が５～４５質量％の粒度範囲からなる、
請求項１に記載のカーボン含有不焼成れんが耐火物。 The refractory raw material is composed of at least one compound selected from Al 2 O 3 and MgO,
The compound has an average particle diameter of 5 to 40% by mass of 3 mm or more, 10 to 45% by mass of 1 mm to less than 3 mm, 15 to 30% by mass of 0.15 mm to less than 1 mm, and 5 to 45% by mass of less than 0.15 mm. consisting of a particle size range of % by weight,
The carbon-containing unburned brick refractory according to claim 1.
前記混合工程で作成された前記混合物と、耐火物原料と、黒鉛原料と、を配合して成形する成形工程と、
を有するカーボン含有不焼成れんが耐火物の製造方法。 a mixing step of mixing a transition metal having an average particle size of 1 μm or less or a transition metal compound containing a transition metal with a liquid binder made of an organic substance to prepare a mixture;
A molding step of blending and molding the mixture prepared in the mixing step, a refractory raw material, and a graphite raw material;
A method for producing a carbon-containing unburned brick refractory.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021209212A JP2023094018A (en) | 2021-12-23 | 2021-12-23 | Carbon-containing non-fired brick refractory and manufacturing method of carbon-containing non-fired brick refractory |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021209212A JP2023094018A (en) | 2021-12-23 | 2021-12-23 | Carbon-containing non-fired brick refractory and manufacturing method of carbon-containing non-fired brick refractory |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2023094018A true JP2023094018A (en) | 2023-07-05 |
Family
ID=87001694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021209212A Pending JP2023094018A (en) | 2021-12-23 | 2021-12-23 | Carbon-containing non-fired brick refractory and manufacturing method of carbon-containing non-fired brick refractory |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2023094018A (en) |
-
2021
- 2021-12-23 JP JP2021209212A patent/JP2023094018A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8450228B2 (en) | Refractory, method for manufacturing refractory, and refractory raw material | |
| Zhu et al. | Heightening mechanical properties and thermal shock resistance of low–carbon magnesia–graphite refractories through the catalytic formation of nanocarbons and ceramic bonding phases | |
| Chen et al. | Effect of Si powder-supported catalyst on the microstructure and properties of Si3N4-MgO-C refractories | |
| Ding et al. | Improved properties of low‐carbon MgO‐C refractories with the addition of multilayer graphene/MgAl2O4 composite powders | |
| Mertke et al. | The influence of nanoparticles and functional metallic additions on the thermal shock resistance of carbon bonded alumina refractories | |
| Liu et al. | A novel approach to prepare graphite nanoplatelets exfoliated by three-roll milling in phenolic resin for low-carbon MgO-C refractories | |
| JP2009221031A (en) | Zirconia-carbon-containing refractory and method for producing the same | |
| JP4394144B2 (en) | Carbon-containing refractory, method for producing the same, and pitch-containing refractory material | |
| Chen et al. | Enhanced performance of low-carbon MgO–C refractories with nano-sized ZrO2–Al2O3 composite powder | |
| JP5192774B2 (en) | Nanocarbon-coated refractory raw material and production method thereof, and refractory using the same and production method thereof | |
| Cao et al. | Influence of sintering process and interfacial bonding mechanism on the mechanical properties of MgO–C refractories | |
| Darban et al. | Characterization of Ni-doped pyrolyzed phenolic resin and its addition to the Al2O3–C refractories | |
| Su et al. | Properties and microstructure evolution of unfired Al–Si incorporated Al2O3–C slide plate materials with trace nano-Al2O3 particles | |
| JP5697210B2 (en) | Converter operating method, magnesia carbon brick used in the converter, manufacturing method of the brick, and lining structure of the converter lining | |
| JP6354073B2 (en) | Carbon-containing fired brick refractories | |
| JP6376102B2 (en) | Carbon-containing unfired brick refractory | |
| KR100914788B1 (en) | Refractory material | |
| JP4791761B2 (en) | Carbon-containing refractories | |
| JP6414000B2 (en) | Method for producing carbon-containing brick refractories | |
| JP2023094018A (en) | Carbon-containing non-fired brick refractory and manufacturing method of carbon-containing non-fired brick refractory | |
| Su et al. | Role of nano-Al2O3 particles in improving the properties of MgO–C slide plate materials | |
| JP2023094019A (en) | Carbon-containing fired brick refractory and manufacturing method of carbon-containing fired brick refractory | |
| JP6414033B2 (en) | Steelmaking smelting vessel | |
| Zang et al. | Study on cobweb‐like carbon nanotubes/calcium aluminate cement and its effect on the properties of Al2O3–SiC–C castables | |
| JP2002316865A (en) | Refractory raw material composition, production method therefor and refractory obtained by forming the composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230724 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20240229 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240326 |