JPH06298572A - Mud material - Google Patents

Mud material

Info

Publication number
JPH06298572A
JPH06298572A JP5087269A JP8726993A JPH06298572A JP H06298572 A JPH06298572 A JP H06298572A JP 5087269 A JP5087269 A JP 5087269A JP 8726993 A JP8726993 A JP 8726993A JP H06298572 A JPH06298572 A JP H06298572A
Authority
JP
Japan
Prior art keywords
mud material
powder
furnace
weight
taphole
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.)
Granted
Application number
JP5087269A
Other languages
Japanese (ja)
Other versions
JP3287905B2 (en
Inventor
Yoshio Omori
平男 大森
Osamu Michihiro
修 道廣
Muneyoshi Katayama
棟義 片山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shinagawa Refractories Co Ltd
Shinagawa Rozai Co Ltd
Original Assignee
Shinagawa Refractories Co Ltd
Shinagawa Rozai Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shinagawa Refractories Co Ltd, Shinagawa Rozai Co Ltd filed Critical Shinagawa Refractories Co Ltd
Priority to JP08726993A priority Critical patent/JP3287905B2/en
Publication of JPH06298572A publication Critical patent/JPH06298572A/en
Application granted granted Critical
Publication of JP3287905B2 publication Critical patent/JP3287905B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Abstract

PURPOSE:To develop a mud material effective for extending the depth of iron spout, uniformizing the structural strength in the iron spout as far as possible at a high level for different temperatures at different depths, improving the abrasion resistance throughout the whole depth range, remarkably improving the durability in combination with the chemical ablation caused by the component constituting the material, reducing the labor for the discharge of iron slag, improving the working environment and prolonging the furnace life. CONSTITUTION:The mud material is produced by compounding a conventional refractory aggregate for mud material with (A) 1-8wt.% of functional phenolic resin fine particles as a sintering material, (B) 1-12wt.% of AN-Si alloy powder or 1-12wt.% of metallic Al powder and metallic Si powder in total and (C) 8-20wt.% of a novolak phenolic resin as a sintering binder.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、マッド材に関するもの
である。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mud material.

【0002】[0002]

【従来の技術】近年、高炉の大型化と高圧操業による出
銑量の増大、微粉炭等の吹き込みによるコークスの大幅
な低減、稼働年数の大幅な延長等の技術革新はマッド材
の使用条件を苛酷なものとし、要求品質は高度化の一途
をたどっている。最近は、作業環境面を考慮した品質ニ
ーズが特に強くなる等要求されるマッド材の具備特性も
変化してきている。
2. Description of the Related Art In recent years, technological innovations such as increasing the amount of tapping due to large-scale blast furnaces and high-pressure operation, drastically reducing coke by blowing pulverized coal, and drastically extending operating years have led to changes in mud material usage conditions. It is harsh and the required quality is becoming higher and higher. Recently, the required characteristics of mud materials have been changing, such as the need for quality in consideration of the work environment has become particularly strong.

【0003】即ち、従来のマッド材は出銑口の閉塞と出
銑、出滓を目的とした安定操業面を主に改善してきた
が、最近では作業量の軽減と作業環境を改善することが
最重要課題であり、また、炉体延命の主要点である出銑
口周辺の炉壁れんがの保護を解決する等のマッド材が要
求されてきている。
That is, the conventional mud material has mainly improved stable operation for the purpose of closing the taphole, tapping and slag, but recently, it has been possible to reduce the work amount and improve the working environment. Mud materials are required to solve the protection of furnace wall bricks around the taphole, which is the most important issue and is the main point of life extension of the furnace body.

【0004】現在の各種高炉は、一炉で1〜4個の冷却
板を備えた出銑口を有し、通常の出銑作業はこれらの出
銑口を交互に使用するため、出銑口の開孔、閉塞の問題
は同一出銑口で通常数時間である。
[0004] Various blast furnaces at present have a taphole equipped with one to four cooling plates in one furnace, and the normal tapping work uses these tapholes alternately. The problem of opening and closing is usually several hours at the same tap.

【0005】しかし、操業法によっては2個の対角線上
の出銑口だけで交互に1週間以上にわたり継続使用し、
その後休止中の出銑口を使用する方法や樋の状況、マッ
ドガンのトラブル等で、1個の出銑口を続けて使用する
連続出銑もあり、その場合は1時間前後で閉塞−開孔を
行なわなければならない時もある。
However, depending on the operating method, only two diagonal tapholes are alternately used continuously for one week or more,
After that, there is also continuous tapping that uses one tapping continuously due to the method of using the tapped hole in the rest, the situation of the gutter, the trouble of the mud gun, etc. Sometimes you have to

【0006】これら操業の多様性からマッド材に要求さ
れる具備特性は、次の点が挙げられる: マッドガンによる出銑口への充填作業を容易にするた
め最適な粘りと可塑性を有すること; 炉内充填直後のマッド材は焼成所要時間が短いほど良
く、開孔時の発煙が少ないこと; 焼成後の焼結強度は、出銑口長さ各部の異なる温度と
焼成時間の長短によって変動が少なく、できるだけ一定
の強度が望ましく、かつ開孔作業が容易であること; 溶滓、溶銑に対して耐食性があり、出銑口の口径拡大
が少なく、安定した出銑速度が維持でき、出銑時間の長
時間化が可能で、1日の出銑回数を低減できること; 炉内充填時において、高温度の旧材との接着性、急加
熱時の容積安定性、早強性に優れ、安定した出銑口深度
を形成維持し、炉壁れんがを保護し得ること; 作業環境を汚染しないこと。
Due to the variety of operations, the mud material is required to have the following characteristics: It has the optimum tenacity and plasticity so as to facilitate the filling work into the taphole by the mud gun; The mud material immediately after filling the inner part should have a shorter firing time and emit less smoke at the time of opening. Sintering strength after firing does not fluctuate due to different temperatures of the taphole length and the firing time. , It is desirable to have a constant strength as much as possible, and it is easy to open holes; corrosion resistance against slag and hot metal, little increase in tap hole diameter, stable tapping speed can be maintained, tapping time The number of pigs per day can be reduced and the number of pig irons per day can be reduced; when filling in the furnace, the adhesiveness with the old material at high temperature, the volume stability at the time of rapid heating, and the fast tapping are stable and stable tapping is possible. Forming and maintaining the mouth depth, It can protect; it does not contaminate the work environment.

【0007】例えば高炉出銑口等に使用されるマッド材
は、上記特性を具備させるため、従来から種々の耐火物
原料や粒度構成、バインダー等が研究されてきた。例え
ばシャモット、ロー石、コークス、粘土を主原料とした
珪酸塩質系、低バン土質系に代わって高バン土アルミ
ナ、電融(または焼結)アルミナ、炭化珪素、窒化珪素、
コークス、粘土を主原料にしたアルミナ質系が主流にな
りつつある。なお、粘結用バインダーとしては、石炭系
タール主体から作業環境の改善を目的に石油系、樹脂系
への転換が図られているのが現状である。
[0007] For example, mud materials used for blast furnace taps and the like have been studied for various refractory raw materials, grain composition, binders, etc. in order to have the above-mentioned characteristics. For example, chamotte, loach, coke, clay-based silicate-based materials, high-ban-soil alumina in place of low-van-soil-based, electro-fused (or sintered) alumina, silicon carbide, silicon nitride,
Alumina based on coke and clay as main raw materials is becoming mainstream. In addition, as a binder for caking, the present situation is that conversion from a coal-based tar-based binder to a petroleum-based or resin-based binder is attempted for the purpose of improving the working environment.

【0008】[0008]

【発明が解決しようとする課題】近年の大型高圧高炉
は、操業経験も数十年を超え、生産技術も非常に高度化
してきた中で作業環境の改善と併せて炉体寿命十数年以
上という稼働年数を目標とすることが一般的になってき
ている。年々操業内容と技術革新が図られ、高炉炉体れ
んがも苛酷な使用条件となってきており、耐用年数の延
長を図らなければならない。
In recent years, large-scale high-pressure blast furnaces have more than several decades of operating experience, and production technology has become extremely sophisticated. It is becoming more common to set a target for such years of operation. The contents of operation and technological innovation are being pursued year by year, and the blast furnace bricks are now under severe usage conditions, and the service life must be extended.

【0009】そのためには炉建設当時に最新の高度技術
を結集しただけでなく、実稼働時の操業技術とマッド材
質の性能を向上させ、安定した出銑口を形成させること
が、好ましい作業環境を造り、より効率的な生産と、炉
体の延命にとって重要である。
For that purpose, it is preferable not only to combine the latest advanced technology at the time of construction of the furnace but also to improve the operation technology and the performance of the mud material at the time of actual operation to form a stable taphole. Is important for more efficient production and life extension of the furnace body.

【0010】作業環境の改善と炉体延命策の中で最も重
要な要因の一つは、出銑口深度の伸長と安定性である。
出銑口深度の伸長と安定性を確保することは、出銑口が
炉内底部に向かって10〜18°傾斜して設置されてい
ることと、長管による流体抵抗も加味して出銑滓時間が
伸びることで出銑滓作業頻度は低減し、また、出銑滓作
業で残銑、残滓量を減少させ、常に低い炉内溶銑レベル
で作業管理することができ、風圧変動の減少及び機器の
故障等による突発休風時の二次的被害の防止等が可能と
なり、操業の安定、安全性の面において大きな役割を果
たすことができる。また、炉体延命策の中で最も重要な
要因の一つは、炉体下部の炉壁れんがの損傷を軽減させ
ることである。炉体下部の炉壁れんがの中で損傷の激し
い部分は貯湯面近傍におけるノラクロ損傷(局部損傷)を
受ける部分で、更に、溶銑、溶滓を排出する出銑口周辺
の損傷が当然ながら最も著しい。従って、出銑口周辺の
炉壁れんがの損傷が、炉体寿命を左右する最大の要因で
あるといっても過言ではない。当該出銑口周辺における
損傷負荷を軽減させる主な対策は、出銑口設置のため炉
体鉄皮を開口している部分があり、冷却板等を埋設して
はいるが、出銑口に向かって炉内の溶銑滓が集中して流
れるため、その溶銑滓の炉体内周辺流れを低減、抑制す
ることで、炉体耐火物と溶銑滓の界面における拡散効果
の抑止と、炉体外水冷効果が向上する結果となり、界面
部の温度低下による反応速度の低減等により炉体下部れ
んがの溶解及び機械的損傷を効率的に低減させ得る。出
銑口近傍の炉体内溶銑滓の周辺流の抑制は出銑口深度を
長くして、できるだけ炉内径中心部より溶銑滓の排出作
業を行うことである。
One of the most important factors in improving the working environment and prolonging the life of the furnace body is the extension and stability of the taphole depth.
To secure the extension and stability of the taphole, the taphole is installed at an angle of 10 to 18 ° toward the bottom of the furnace, and the fluid resistance due to the long pipe is also taken into consideration. As the slag time is extended, the frequency of tapping slag work is reduced, and the amount of residual pig iron and residual slag is reduced in the tapping slag work, so that the work can be managed at a constantly low level of hot metal in the furnace, which reduces wind pressure fluctuation It is possible to prevent secondary damages due to sudden wind breaks due to equipment failure, etc., and play a major role in terms of operational stability and safety. Moreover, one of the most important factors in the life extension measures of the furnace body is to reduce the damage of the furnace wall brick under the furnace body. The severely damaged part of the furnace wall brick in the lower part of the furnace body is the part that is subject to norachrome damage (local damage) near the hot water storage surface, and of course the damage around the taphole that discharges hot metal and molten slag is most significant. . Therefore, it is no exaggeration to say that damage to the furnace wall brick around the taphole is the most important factor affecting the life of the furnace body. The main measure to reduce the damage load around the taphole is that there is a part where the furnace shell is opened to install the taphole and the cooling plate etc. are buried. Since the molten iron in the furnace flows in a concentrated manner toward the furnace, the flow of the molten iron around the furnace is reduced and suppressed to suppress the diffusion effect at the interface between the furnace refractory and the molten iron and to cool the water outside the furnace. As a result, the melting rate and mechanical damage of the lower bricks of the furnace body can be efficiently reduced by reducing the reaction rate due to the temperature decrease at the interface. Suppressing the flow around the molten iron slag in the furnace near the taphole is to increase the taphole depth and discharge the molten pigtail from the center of the furnace as much as possible.

【0011】従って、マッド材の役割は、安定した出銑
口と深度を維持することが、出銑滓作業の改善と炉体下
部出銑口周辺のれんが保護にあるといっても過言ではな
い。
Therefore, it is not an exaggeration to say that the role of the mud material is to maintain a stable taphole and depth, to improve the tapping work and to protect the goodwill around the lower taphole of the furnace body. .

【0012】しかし、現在のマッド材は材質の改善と進
歩はなされているが、炉内の内容物の動きや溶銑滓の激
しい流下に対して充分に満足できる安定した出銑口深度
とその性能が得られず、マッド材の多量の充填や設備的
に出銑口上部の羽口内径の縮小や、羽口の閉塞、羽口間
隔を広げたりして対応しているのが現状である。
However, although the current mud materials have been improved and improved, the stable taphole depth and its performance which are sufficiently satisfied with respect to the movement of the contents in the furnace and the violent downflow of the molten pig iron and its performance. However, the present situation is to cope with the problem by filling a large amount of mud material, reducing the inner diameter of the tuyere at the upper taphole, closing the tuyere, and widening the tuyere spacing in terms of equipment.

【0013】これらの対策で、マッド材充填量の増加
は、焼成不足による発煙の増大や作業環境の悪化を招
き、また、設備面で対応すれば、炉内の風量バランスが
損なわれる等で好ましくない。従って、高炉操作技術に
適合したマッド材を開発し、出銑口深度を伸長させ、安
定した出銑滓作業を営み、かつ長時間出銑を可能にし、
1日の出銑回数の低減を図り、出銑滓作業の軽減と環境
改善することが最も重要な課題である。
With these measures, an increase in the filling amount of the mud material causes an increase in smoke generation and a deterioration of the working environment due to insufficient firing, and if the equipment is dealt with, the air flow rate balance in the furnace is impaired. Absent. Therefore, we developed a mud material suitable for blast furnace operation technology, extended the taphole depth, carried out stable tapping work, and enabled long-time tapping.
One of the most important issues is to reduce the number of pigs per day, reduce the amount of pig iron slag work, and improve the environment.

【0014】従来、作業環境の改善策として、マッド材
の粘結用バインダーは石炭タール系から樹脂系に変える
ことが提案され、発煙、悪臭の軽減、早期強度の発現と
焼成時間の短縮が図られ、出銑口の充填作業の環境改善
と作業時間の短縮等の改善がなされてきた。
Conventionally, as a measure for improving the working environment, it has been proposed to change the binder for binding mud materials from a coal tar type to a resin type, which aims to reduce smoking, foul odor, early development of strength and reduction of firing time. As a result, improvements have been made in the environment for filling the taphole, such as shortening the working time.

【0015】しかし、出銑口内に充填されたマッド材
は、高炉操業上、炉外側から炉内深部に向かって温度勾
配が300〜400℃から炉内深度先端部で1500℃
以上の範囲があり、深度各部のマッド材焼結強度は必ず
しも満足できるものてはなく、かつ技術的に低中間温度
域の連続した高い強度を充分になし得なかったので、そ
れに起因する問題も多くあった。
However, in the blast furnace operation, the mud material filled in the taphole has a temperature gradient of 300 to 400 ° C. from the outside of the furnace to the deep inside of the furnace to 1500 ° C. at the front end of the inside of the furnace.
There is the above range, the mud material sintering strength at each depth is not always satisfactory, and technically it was not possible to sufficiently achieve continuous high strength in the low intermediate temperature range, so there are also problems caused by it. There were many.

【0016】また、最近、作業環境面から主流になりつ
つある樹脂系マッド材は、ヘキサメチレンテトラミンや
レゾール等を硬化促進剤として使用すれば、300℃付
近の低温強度は高められるが、それ以上の温度になるに
従ってその強度は低下傾向の度合を増大させ、1000
℃以上になって耐火物の焼結開始により強度は徐々に上
昇するが、深度構成体内で組織的強度の弱い部分が存在
し、組織体の線膨張も収縮傾向が強くなり、かつ組織内
の粒境界周辺に空隙や内在微小亀裂が発生し、開孔作業
時に割れ易く、出銑滓作業のトラブルになり易い。
In addition, resin mud materials, which have recently become the mainstream in terms of working environment, can be improved in low temperature strength around 300 ° C. by using hexamethylenetetramine, resole or the like as a curing accelerator. The strength increases with decreasing temperature and the degree of decrease tends to 1000
At temperatures above ℃, the strength gradually increases due to the start of sintering of the refractory, but there is a part with weaker structural strength in the depth structure, and the linear expansion of the tissue also tends to contract, and Voids and internal microcracks are generated around the grain boundaries, which easily breaks during the opening work and causes troubles during the tapping work.

【0017】また、硬化促進剤を使用し、熱硬化性を顕
著にすると、炉内の赤熱された堆積マッド材との接着性
を阻害し、出銑口深度は伸長し難くなる。
Further, when a curing accelerator is used to make the thermosetting property remarkable, the adhesion property with the red-heated accumulated mud material in the furnace is impeded, and the tap hole depth becomes difficult to extend.

【0018】従来、マッド材の高耐用性化は、高耐食性
になればなる程、慣用のマッド材用耐火組成物は高融点
の高純度のアルミナやアルミナスピネル、炭化珪素、窒
化珪素、コークス等が主体となり、比較的低融点の粘土
や珪酸塩鉱物の含有量は化学的溶損の点から最少限に抑
える傾向にあり、従って、耐火組成物の焼結はし難くな
る方向は否めないし、焼結用バインダーから得られる強
度発現にも限界があり、深度各部の異なった温度に対す
る強度を任意に調整できるまでに至っていないのが現状
である。
Conventionally, the higher the durability of mud material is, the higher the corrosion resistance is, the more conventional the refractory composition for mud material is, the more pure high melting point alumina, alumina spinel, silicon carbide, silicon nitride, coke, etc. The content of clay and silicate minerals having a relatively low melting point tends to be minimized from the viewpoint of chemical erosion, and therefore, it cannot be denied that the refractory composition is difficult to sinter, There is a limit to the strength development that can be obtained from the binder for sintering, and it is the current situation that the strength of each depth portion at different temperatures cannot be adjusted arbitrarily.

【0019】従って、本発明の目的は、出銑口深度の伸
長が可能で、かつ深度各部の異なった温度に対して出銑
口内の組織強度を高強度化した中で極力平準化させるこ
とが、深度全長における耐摩耗性の向上が図られ、材質
構成成分による化学溶損と併せて耐用性を大幅に改善
し、出銑滓作業の軽減と環境改善と炉体延命をなし得る
マッド材を開発することにある。
Therefore, it is an object of the present invention to extend the taphole depth and to level the tissue strength in the taphole as much as possible while increasing the tissue strength in the taphole at different temperatures. In addition, a mud material that has improved wear resistance over the entire depth and has significantly improved durability in addition to chemical erosion due to material constituents, can reduce the work of tapping waste, improve the environment and prolong the life of the furnace body. To develop.

【0020】[0020]

【課題を解決するための手段】本発明に係るマッド材
は、慣用のマッド材用耐火物骨材に、焼結材として機能
性微粒子状フェノール樹脂を1〜8重量%及びAl−S
i系合金粉末を1〜12重量%または金属Al粉末及び
金属Si粉末を合計量で1〜12重量%、及び焼結用バ
インダーとしてノボラック型フェノール樹脂8〜20重
量%添加、配合することを特徴とする。
The mud material according to the present invention comprises a refractory aggregate for a conventional mud material, 1 to 8% by weight of functional particulate phenolic resin and Al-S as a sintering material.
1 to 12% by weight of i-based alloy powder or 1 to 12% by weight of metal Al powder and metal Si powder in total, and 8 to 20% by weight of novolac type phenol resin as a binder for sintering are added and blended. And

【0021】[0021]

【作用】本発明のマッド材は、深度各部の異なった温度
に対する強度を任意に発現する方法として、特に300
〜1000℃の範囲を機能性微粒子状フェノール樹脂を
使用することにより強固で均一な炭素結合を、700℃
以上の範囲では金属から炭化物の生成による結合を、即
ち、Al−Si系合金粉末または金属Al粉末及び金属
Si粉末の適用で700℃以上の範囲では金属アルミニ
ウム成分で炭化物を、1300℃以上の範囲を金属シリ
コン成分による炭化物を出銑口深度内各部の異なった還
元雰囲気温度帯で生成させマッド材組織強度を任意に高
めることを可能にしたものである。
The mud material of the present invention has a strength of 300 degrees as a method of arbitrarily expressing strength at different depths at different temperatures.
By using a functional fine particle phenolic resin in the range of up to 1000 ° C, a strong and uniform carbon bond can be obtained at 700 ° C.
In the above range, the bond due to the formation of the carbide from the metal, that is, in the range of 700 ° C. or higher in the range of 700 ° C. or higher by applying the Al—Si alloy powder or the metallic Al powder and the metal Si powder, the range of 1300 ° C. or higher in the carbide of the metal aluminum component. It is possible to arbitrarily increase the structure strength of the mud material by generating carbides of metallic silicon components at different temperature ranges of reducing atmosphere in each part within the taphole depth.

【0022】即ち、本発明は粒度調整した電融アルミ
ナ、焼結アルミナ、ボーキサイト、バン土頁岩、アルミ
ナスピネル、ロー石、炭化珪素、窒化珪素、炭素材及び
粘土等より構成された慣用のマッド材用耐火物骨材に、
焼結材として機能性微粒子状フェノール樹脂を1〜8重
量%、及びAl−Si系合金粉末または金属Al粉末及
び金属Si粉末を1〜12重量%、焼結用バインダーと
してノボラック型フェノール樹脂8〜20重量%を使用
することを特徴としたマッド材に係る。
That is, the present invention is a conventional mud material composed of fused-grain alumina, sintered alumina, bauxite, shale shale, alumina spinel, lozenge, silicon carbide, silicon nitride, carbon material, clay, etc., whose particle size is adjusted. For refractory aggregates for
1 to 8% by weight of functional fine particle phenol resin as a sintering material, 1 to 12% by weight of Al-Si alloy powder or metal Al powder and metal Si powder, and novolac type phenol resin 8 to 8 as a binder for sintering. It relates to a mud material characterized by using 20% by weight.

【0023】本発明のマッド材に用いる焼結材の中で、
低温度域(300〜1000℃)における強度発現に効果
的な機能性微粒子状フェノール樹脂は、重量平均分子量
10000を超えるもので、ベンゼン環1個当たりメチ
ロール基0.1〜0.3個を含有した高分子樹脂の中で、
メタノール溶剤に対する煮沸溶解量が40重量%以上も
のである。
Among the sintered materials used for the mud material of the present invention,
The functional fine particle phenol resin effective for strength development in a low temperature range (300 to 1000 ° C) has a weight average molecular weight of more than 10,000 and contains 0.1 to 0.3 methylol groups per benzene ring. Among the polymer resins
The boiling dissolution amount in a methanol solvent is 40% by weight or more.

【0024】なお、アセトン溶剤に対しては、室温で2
4時間経過後の溶解量が50重量%未満のものが、粘結
用バインダーとの結合と炭化過程における容積変化を減
少させる点において好ましい。
It should be noted that, for an acetone solvent, 2 at room temperature.
It is preferable that the amount of dissolution after 4 hours is less than 50% by weight from the viewpoint of reducing the volume change in the binding process with the binder for binding and the carbonization process.

【0025】前記機能性微粒子状フェノール樹脂は、分
子構造内に適度のメチロール基を有しているため、緩慢
な熱硬化性状と粘結用バインダーとして用いるノボラッ
ク型フェノール樹脂等の他の樹脂に対して、親和性や反
応性に優れた特性があり、かつ残炭量は70重量%以上
と非常に高いことから、マッド材組織内に均質な架橋構
造を呈し、この架橋構造は、炭化においても高残炭で、
而も均質で強固なC−C結合を形成し得るので、従来の
一般的なノボラック型フェノール樹脂粉末や石炭ピッチ
や石油ピッチの添加では、特に300〜1000℃付近
の低温度域の強度は弱く、脆弱であった点を解決したも
のである。また、緩慢な熱硬化性状は、炉内の赤熱され
た堆積マッド材との接着を阻害することなく、優れた接
着性を有している。
Since the functional fine-particle phenol resin has an appropriate methylol group in the molecular structure, it has a slow thermosetting property and is no different from other resins such as novolac type phenol resin used as a binder for binding. Since it has excellent affinity and reactivity, and the residual carbon content is very high at 70% by weight or more, it exhibits a homogeneous crosslinked structure in the mud material structure. With high residual coal,
Further, since a homogeneous and strong C—C bond can be formed, the strength of the conventional general novolac type phenol resin powder, coal pitch and petroleum pitch is weak especially in the low temperature region around 300 to 1000 ° C. , Is a solution to the weak point. Further, the slow thermosetting property has excellent adhesiveness without hindering the adhesion with the red-heated accumulated mud material in the furnace.

【0026】一方、700℃付近から上の温度帯の強度
発現は、Al−Si系合金粉末または金属Al粉末及び
金属Si粉末の添加により、金属アルミニウム成分から
還元雰囲気中でAl43等の炭化物を、金属シリコン成
分は1300℃以上でSiC等の炭化物を生成すること
と、耐火物組成物中のSiO2成分が一部金属アルミニ
ウムによって還元され、SiC成分等を生成するため、
これらの炭化物生成が耐火物の組織の結合力に寄与し、
耐火物自体の焼結と併せて、目標とする任意の強度に調
整することを可能にならしめたものである。
On the other hand, the strength development in the temperature range from about 700 ° C. to the upper part is expressed by adding Al—Si alloy powder or metallic Al powder and metallic Si powder to produce Al 4 C 3 or the like from a metallic aluminum component in a reducing atmosphere. As for the carbide, the metal silicon component produces carbides such as SiC at 1300 ° C. or higher, and the SiO 2 component in the refractory composition is partially reduced by metallic aluminum to produce the SiC component and the like.
The formation of these carbides contributes to the cohesive strength of the refractory structure,
It is possible to adjust the strength to a desired value together with the sintering of the refractory itself.

【0027】該機能性微粒子状フェノール樹脂に比較し
て、従来の一般的なノボラック型フェノール樹脂粉末は
重量平均分子量300〜800で、ベンゼン環1個当た
りメチロール基0〜0.01個と機能性微粒子状フェノ
ール樹脂の約10分の1以下と極端に少なく、そのため
熱硬化性に乏しく、重合から炭化過程に起きる分解で残
炭量も50重量%未満と少なく、C−C結合も不均質で
充分な強度は得られなかった。また、レゾール型フェノ
ール樹脂は、メチロール基がベンゼン環1個当たり1〜
3個と多過ぎて、熱硬化速度が非常に速く、加熱される
過程で架橋構造に密な部分と粗な部分ができ、不均質な
C−C結合を呈し、かつ熱硬化速度が速過ぎると、熱間
における接着性を阻害するといった点で好ましくない。
In comparison with the functional fine particle phenol resin, the conventional general novolac type phenol resin powder has a weight average molecular weight of 300 to 800 and a functionality of 0 to 0.01 methylol groups per benzene ring. It is extremely less than about one-tenth or less of the particulate phenolic resin, so it has poor thermosetting properties, the amount of residual carbon is less than 50% by weight due to the decomposition that occurs in the carbonization process from polymerization, and the C--C bond is also inhomogeneous. Sufficient strength was not obtained. The resol type phenol resin has a methylol group of 1 to 1 per benzene ring.
There are too many three, the heat curing rate is very fast, and dense and coarse portions are formed in the crosslinked structure in the process of heating, exhibiting inhomogeneous CC bonds, and the heat curing rate is too fast. That is, it is not preferable in that the adhesiveness during hot is impaired.

【0028】該機能性微粒子状フェノール樹脂の特性値
の中で、メタノール溶剤に対する煮沸溶解量が40重量
%未満の場合は、該機能性微粒子状フェノール樹脂の熱
溶融性と自硬化性が低下し、かつマッド材に粘結材用バ
インダーとして添加するノボラック型フェノール樹脂と
の親和性や反応性が損なわれ、不充分なC−C結合にな
るため、充分なC−C結合の強度が得られないと言った
不都合がある。
When the boiling dissolution amount in a methanol solvent is less than 40% by weight among the characteristic values of the functional fine particle phenol resin, the heat melting property and the self-curing property of the functional fine particle phenol resin are deteriorated. In addition, the affinity and reactivity with the novolak type phenolic resin added as a binder for the mud material to the mud material are impaired, resulting in insufficient C—C bond, so that sufficient C—C bond strength is obtained. There is an inconvenience to say.

【0029】また、添加量が1〜8重量%の適用範囲外
では、例えば1重量%未満の場合、強度の発現効果が弱
く、8重量%を超えると耐火物組織体としての線膨張率
が負傾向の度合いが大きくなり、かつ粘性が強くなり過
ぎてマッドガンによる充填作業を困難にすると言った等
の不都合が生じる。
If the amount added is outside the applicable range of 1 to 8% by weight, for example, if it is less than 1% by weight, the effect of developing strength is weak, and if it exceeds 8% by weight, the linear expansion coefficient of the refractory structure is high. There is an inconvenience such that the degree of the negative tendency becomes large and the viscosity becomes too strong, which makes the filling work by the mud gun difficult.

【0030】また、700℃以上の温度領域で焼結強度
を発現させる目的で用いるAl−Si系合金粉末または
金属Al粉末または金属Si粉末は、粒度が100メッ
シュ以上と粗くなると、耐火物構成体内における微小組
織への分散性と反応性が損なわれるため好ましくない。
Further, the Al--Si alloy powder, the metal Al powder, or the metal Si powder used for the purpose of developing the sintering strength in the temperature range of 700 ° C. or higher has a coarse particle size of 100 mesh or more, and the refractory structure is It is not preferable because the dispersibility in the microstructure and the reactivity in the above are impaired.

【0031】Al−Si系合金粉末のAl成分の含有比
率は、Al−Si二成分系合金の状態図から明らかなよ
うに、88重量%付近の共晶点で融点が約577℃と最
も低く、そのような中温度領域から上において、Al系
炭化物の生成反応が活性となり、更に、Si成分が増す
に従い、Siの融点に近付き高くなり、Si成分の含有
量が60重量%付近に達すると融点が約1130℃とな
る。従って、出銑口内の温度帯の中で700〜1300
℃の範囲内における焼結強度を得るために最適である。
まだ、マッド材用耐火物骨材の焼結反応が充分起きない
1000℃までの温度範囲の焼結強度を特に得るため、
Al成分比が40〜90重量%必要である。Al成分比
が40重量%未満では700〜1000℃の範囲の充分
な強度が得られない。一方、Si成分について言及する
と、マッド材構成耐火物中の粘土やSiO2の含有量が
多い珪酸塩鉱物等は、1000℃付近から徐々に焼結が
進行し始めるが、これら珪酸塩鉱物は耐溶損性の点から
好ましくなく、SiO2の含有量を減少させた高融点の
高アルミナ質耐火骨材が一般的に採用される傾向にあ
り、耐火物自体の焼結はし難い方向にある。従って、1
300℃以上の領域で焼結強度を発現させるために、A
l−Si系合金中のSi成分は10〜60重量%含有し
ていることが必要であり、それ以外の範囲では、700
〜1300℃の強度と1300℃以上の強度のバランス
が損なわれ好ましくない。また、金属Al粉末と金属S
i粉末を併用する場合にも、Al成分とSi成分の構成
比は上述に準ずる。
As is clear from the phase diagram of the Al-Si binary alloy, the content ratio of the Al component in the Al-Si alloy powder is the lowest at the eutectic point near 88% by weight, which is about 577 ° C. From above such an intermediate temperature range, the reaction of forming Al-based carbide is activated, and as the Si component increases, the melting point of Si approaches and becomes higher, and when the content of the Si component reaches around 60% by weight. The melting point is about 1130 ° C. Therefore, 700 to 1300 in the temperature zone inside the taphole
It is most suitable for obtaining the sintering strength in the range of ° C.
In order to obtain the sintering strength especially in the temperature range up to 1000 ° C where the sintering reaction of the refractory aggregate for mud material does not sufficiently occur,
The Al component ratio is required to be 40 to 90% by weight. If the Al component ratio is less than 40% by weight, sufficient strength in the range of 700 to 1000 ° C cannot be obtained. On the other hand, referring to the Si component, clay and silicate minerals having a high SiO 2 content in the mud material refractory gradually start to sinter at around 1000 ° C. A high-alumina refractory aggregate having a high melting point and a reduced SiO 2 content tends to be generally adopted from the point of view of loss, and it is difficult to sinter the refractory itself. Therefore, 1
In order to develop the sintering strength in the range of 300 ° C or higher, A
It is necessary that the Si component in the 1-Si-based alloy be contained in an amount of 10 to 60% by weight, and in other ranges, 700
The balance between the strength of 1300 ° C and the strength of 1300 ° C or higher is unfavorable. Also, metal Al powder and metal S
Even when i powder is used together, the composition ratio of the Al component and the Si component is in accordance with the above.

【0032】また、Al−Si系合金粉末の添加量また
は金属Al粉末と金属Si粉末の合計添加量が1重量%
未満の場合は、焼結強度を高める効果は期待できない
し、添加量が12重量%を超えると、700℃以上の強
度が高くなり過ぎて、現在の高性能の開孔機を使用して
も、出銑口の開孔が困難になり、出銑口の深度を形成し
ているマッド材が開口時の抵抗で割れる等の不都合を生
じ好ましくない。
The addition amount of the Al--Si alloy powder or the total addition amount of the metal Al powder and the metal Si powder is 1% by weight.
If it is less than the above, the effect of enhancing the sintering strength cannot be expected, and if the addition amount exceeds 12% by weight, the strength of 700 ° C. or higher becomes too high, and even if the present high-performance opener is used. However, it is not preferable because the opening of the taphole becomes difficult and the mud material forming the depth of the taphole is broken by the resistance at the time of opening.

【0033】なお、本発明に用いる粘結用バインダーで
あるノボラック型フェノール樹脂の添加量は、8〜20
重量%の範囲が好ましく、8重量%未満ではマッドガン
による出銑口への充填作業性が悪くなり、20重量%を
超えると焼成後のマッド材組織が粗雑化し、耐用性を低
下せることから好ましくない。
The addition amount of the novolac type phenol resin which is the binder for caking used in the present invention is 8 to 20.
A range of 10% by weight is preferable, and if less than 8% by weight, the workability of filling the taphole with a mud gun becomes poor, and if more than 20% by weight, the structure of the mud material after firing becomes coarse and durability is reduced, which is preferable. Absent.

【0034】[0034]

【実施例】以下に実施例及び比較例を挙げて本発明を更
に説明する。 実施例 以下の表1は炭素結合を目的とした結合材の特性を示
し、表2はAl−Si系合金の特性を示すものである。
表3は耐火骨材として使用した原料の化学成分と粒度を
示し、表4は実施例及び比較例の配合を示すものであ
る。なお、表中の記号KBF樹脂は、機能性微粒子状フ
ェノール樹脂(カネボウ社製−商品名:ベルパール)を、
N型F樹脂は一般市販品ノボラック型フェノール樹脂を
それぞれ示すものである。
EXAMPLES The present invention will be further described below with reference to Examples and Comparative Examples. Examples Table 1 below shows the characteristics of the binder for carbon bonding, and Table 2 shows the characteristics of the Al-Si alloy.
Table 3 shows the chemical composition and particle size of the raw material used as the refractory aggregate, and Table 4 shows the composition of the examples and comparative examples. In addition, the symbol KBF resin in the table is a functional fine particle phenol resin (Kanebo Corporation-trade name: Bell Pearl),
The N-type F resin is a general commercial novolak type phenol resin.

【0035】[0035]

【表1】 [Table 1]

【0036】[0036]

【表2】 [Table 2]

【0037】[0037]

【表3】 [Table 3]

【0038】[0038]

【表4】 [Table 4]

【0039】[0039]

【表5】 [Table 5]

【0040】表4に示す各特性比較についてのテスト方
法を以下に説明する。 各特性値の測定に供する試料は、各配合について、加
熱式下廻りミキサーを用いて、粘結用バインダーとして
N型F樹脂溶液を使用し、練土温度を30〜40℃に保
ち、よく混練して供試体成形用の杯土とした。 物理特性値は、形状35×35×140mm、成形圧
力14.7MPaで作成し、供試体とした。 耐食性比較:*1は高周波誘導炉式侵食試験法で15
50℃×3時間、侵食剤として銑鉄10kgと高炉スラ
グ300g×6回入れ替えによる最大侵食深さを指数表
示したものであり、*2はアーク式回転ドラム侵食試験
法で1550℃×3時間、侵食剤として銑鉄2kgと高
炉スラグ800g×3回入れ替えによる最大侵食深さを
指数表示したものであり、耐用性を比較した。 熱硬化速度:*5は成形圧力14.7MPaで、50
mmφ×50mmhに成形したマッド材ブリケットを2
kwの螺旋状電気ヒーター300mmφの上に、鉄板
(9mm×350mm×350mm)を置き、その鉄板の
表面温度を500℃に保持し、該鉄板上にブリケットを
載せ、上部まで硬化するに必要な時間を求め、熱硬化速
度として比較した。
The test method for each characteristic comparison shown in Table 4 will be described below. The samples to be used for the measurement of each characteristic value are, for each composition, using a heating type lower mixer, using an N-type F resin solution as a binder for binding, keeping the dough temperature at 30 to 40 ° C., and thoroughly kneading. And used as the clay for molding the specimen. Physical property values were created with a shape of 35 × 35 × 140 mm and a molding pressure of 14.7 MPa, and used as a test piece. Corrosion resistance comparison: * 1 is 15 for high frequency induction furnace type erosion test method
50 ° C x 3 hours, 10 kg of pig iron as an erosion agent and 300 g of blast furnace slag x 6 times are the maximum erosion depths expressed as an index, * 2 is the arc type rotary drum erosion test method at 1550 ° C x 3 hours, erosion 2 kg of pig iron as an agent and 800 g of blast furnace slag × 3 times the maximum erosion depth by exchanging 3 times are shown as an index, and the durability was compared. Thermosetting speed: * 5 is 50 at a molding pressure of 14.7 MPa
2 pieces of mud material briquette molded to mmφ x 50 mmh
Iron plate on 300mmφ kW spiral electric heater
(9 mm × 350 mm × 350 mm) was placed, the surface temperature of the iron plate was kept at 500 ° C., a briquette was placed on the iron plate, and the time required for curing to the upper part was obtained and compared as a heat curing rate.

【0041】本発明品3のマッド材を大型高圧高炉(容
積4550m3)において実用テストした結果、比較品1
4に対して使用14日間(1キャンペーン)の平均値で出
銑時間は、162分が217分と大幅に延長し、出銑口
深度においても、3400mmが3510mmと伸長し
た。従って、本発明品のマッド材が主眼とした出銑口深
度内各部の異なった温度帯の強度を任意に発現させ平準
化させることで、耐食性要因の1つである摩耗損傷が改
善でき、かつKBF樹脂の緩慢な硬化性状により熱間に
おける接着性を阻害することなく深度伸長に繋がった等
が実証でき、併せて作業環境の改善が達成できる等画期
的なマッド材を開発することができた。
As a result of a practical test of the mud material of the product 3 of the present invention in a large high-pressure blast furnace (volume 4550 m 3 ), Comparative product 1
On the other hand, the average tapping time of 14 days (1 campaign) was 162 minutes, which was 217 minutes, and the depth of tapping was 3400 mm and 3510 mm. Therefore, by arbitrarily expressing and leveling the strength of different temperature zones of the respective parts within the taphole depth, which is the main object of the mud material of the present invention, wear damage, which is one of the corrosion resistance factors, can be improved, and It is possible to demonstrate that the slow curing property of KBF resin led to depth extension without hindering the adhesiveness during hot work, and at the same time, it was possible to develop an epoch-making mud material that can improve the working environment. It was

【0042】[0042]

【発明の効果】本発明のマッド材は、高炉出銑口深度内
各部の異なった温度帯の強度を任意の高い数値の強度に
発現させ、かつ強度の平準化をさせることを可能にし
た。これによって最近のマッド材が高耐食性化の追及に
より、高純度高融点の耐火物指向になり、そのため耐火
物組織の焼結はし難く、耐食性要因の耐溶損性と耐摩耗
性損傷のうち、耐溶損性は改善されてきてはいるが、特
に出銑口のような使用条件では、もう一つの要因である
摩耗損傷を改善することが最も重要であり、本発明はこ
の点を解決したものである。また、炉内の灼熱されたマ
ッド材との接着性と急加熱に伴うマッド材中の揮発分の
急激なガス化による組織の粗雑化や崩壊現象を防止する
ために適度の緩慢な熱硬化性を、特定の樹脂を使用する
ことで優れた特性をなし得たので、出銑口深度の伸長と
安定維持を可能なものとし、かつ作業環境と閉塞及び開
孔準備作業等の面で大幅な改善が図られ、毎日の軽快な
出銑作業と高炉炉体下部のれんが保護による高炉稼働年
数の延長ができる。また、本発明のマッド材は、高炉出
銑口閉塞の目的だけではなく、電気炉の出銑口の閉塞材
や溶湯を扱う湯口の閉塞等にも応用できる。
EFFECTS OF THE INVENTION The mud material of the present invention makes it possible to express the strengths of different temperature zones at the respective parts within the taphole depth of the blast furnace to arbitrarily high strengths and level the strengths. Due to this, the recent mud materials have become highly refractory-oriented with high purity and high melting point due to the pursuit of high corrosion resistance, so it is difficult to sinter the refractory structure, and among the corrosion resistance factors of melt damage resistance and wear resistance damage, Although the erosion resistance has been improved, it is most important to improve the wear damage, which is another factor, especially under the use conditions such as tapping, and the present invention solves this point. Is. In addition, the adhesiveness with the burning mud material in the furnace and the moderate slow thermosetting property to prevent the coarsening and collapse phenomenon of the structure due to the rapid gasification of volatile components in the mud material due to rapid heating , It was possible to achieve excellent characteristics by using a specific resin, which enables the depth of taphole to be extended and maintain stable, and it is possible to significantly reduce the work environment, blockage, and preparation work for holes. Improvements have been made, and daily light tapping work and protection of bricks at the bottom of the blast furnace furnace body can extend the blast furnace operating years. Further, the mud material of the present invention can be applied not only for the purpose of blocking the tap hole of the blast furnace, but also for closing the tap hole of the electric furnace and the gate for handling molten metal.

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 慣用のマッド材用耐火物骨材に、焼結材
として機能性微粒子状フェノール樹脂を1〜8重量%及
びAl−Si系合金粉末を1〜12重量%または金属A
l粉末及び金属Si粉末を合計量で1〜12重量%、及
び焼結用バインダーとしてノボラック型フェノール樹脂
8〜20重量%添加、配合することを特徴とするマッド
材。
1. A conventional refractory aggregate for mud material, containing 1 to 8% by weight of functional fine particle phenolic resin and 1 to 12% by weight of Al-Si alloy powder or metal A as a sintering material.
1 to 12% by weight in total of 1 powder and metallic Si powder, and 8 to 20% by weight of novolac type phenol resin as a binder for sintering, and mixed.
JP08726993A 1993-04-14 1993-04-14 Mud wood Expired - Fee Related JP3287905B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP08726993A JP3287905B2 (en) 1993-04-14 1993-04-14 Mud wood

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP08726993A JP3287905B2 (en) 1993-04-14 1993-04-14 Mud wood

Publications (2)

Publication Number Publication Date
JPH06298572A true JPH06298572A (en) 1994-10-25
JP3287905B2 JP3287905B2 (en) 2002-06-04

Family

ID=13910052

Family Applications (1)

Application Number Title Priority Date Filing Date
JP08726993A Expired - Fee Related JP3287905B2 (en) 1993-04-14 1993-04-14 Mud wood

Country Status (1)

Country Link
JP (1) JP3287905B2 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105418091A (en) * 2015-11-27 2016-03-23 蚌埠海明压铸机有限公司 Hydration-resistant fireproof material
CN105439580A (en) * 2015-11-27 2016-03-30 蚌埠海明压铸机有限公司 High-performance refractory material
CN105439583A (en) * 2015-11-30 2016-03-30 蚌埠市华科机电有限责任公司 Quartz sand fire-resisting material
CN105439584A (en) * 2015-11-30 2016-03-30 蚌埠市华科机电有限责任公司 High-quality refractory material

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