JPH0777981B2 - High corrosion resistance silicon carbide / alumina brick - Google Patents

High corrosion resistance silicon carbide / alumina brick

Info

Publication number
JPH0777981B2
JPH0777981B2 JP3271180A JP27118091A JPH0777981B2 JP H0777981 B2 JPH0777981 B2 JP H0777981B2 JP 3271180 A JP3271180 A JP 3271180A JP 27118091 A JP27118091 A JP 27118091A JP H0777981 B2 JPH0777981 B2 JP H0777981B2
Authority
JP
Japan
Prior art keywords
silicon carbide
brick
weight
alumina
corrosion resistance
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.)
Expired - Fee Related
Application number
JP3271180A
Other languages
Japanese (ja)
Other versions
JPH05105507A (en
Inventor
健 西原
一巳 戸川
英昭 西山
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
Original Assignee
Shinagawa Refractories 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 filed Critical Shinagawa Refractories Co Ltd
Priority to JP3271180A priority Critical patent/JPH0777981B2/en
Publication of JPH05105507A publication Critical patent/JPH05105507A/en
Publication of JPH0777981B2 publication Critical patent/JPH0777981B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Compositions Of Oxide Ceramics (AREA)

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、高耐食性炭化珪素・ア
ルミナ質れんがに関し、更に詳細には焼却炉または焼却
灰溶融炉用高耐食性炭化珪素・アルミナ質れんがに関
る。
BACKGROUND OF THE INVENTION This invention related to the high corrosion resistance of silicon carbide, alumina bricks, more particularly incinerator or incineration
Ru related to <br/> the high corrosion resistance of silicon carbide, alumina brick for ash melting furnace.

【0002】[0002]

【従来の技術】従来、炭化珪素を含む耐火れんがは、一
般にSiCの含量が90%前後の高純度のものが使用さ
れている。この高純度炭化珪素れんがは、溶融金属ある
いは溶融焼却灰の付着防止、熱的スポーリングなどによ
る損傷防止に極めて有効である。
2. Description of the Related Art Conventionally, refractory bricks containing silicon carbide have generally been of high purity with a SiC content of about 90%. This high-purity silicon carbide brick is extremely effective in preventing adhesion of molten metal or molten incineration ash, and preventing damage due to thermal spalling and the like.

【0003】しかし、このような高純度炭化珪素れんが
は使用中の加熱により残存線膨張収縮の体積変化が起こ
り易い。これはSiCの酸化膨大及び焼失によるものと
考えられており、特に、1100℃以上の高温状態で生
じ易い。また、高純度炭化珪素れんがは熱伝導率が金属
なみに高いため、また、れんが炉外側の面も炉内温度と
ほとんど変わらないため、放散熱量が大きく、熱エネル
ギーのロスという欠点もある。更に、SiC原料は非常
に高価であるため、高純度炭化珪素れんがは一般に用い
られる耐火れんがに比して非常に高価なものとなる。
However, such a high-purity silicon carbide brick is likely to undergo residual linear expansion / contraction volume change due to heating during use. This is considered to be due to the swelling and burning of SiC, and is particularly likely to occur at a high temperature of 1100 ° C. or higher. Further, since the high-purity silicon carbide brick has a high thermal conductivity as high as that of a metal, and since the surface of the brick outside the furnace is almost the same as the temperature inside the furnace, the amount of heat dissipated is large and the heat energy is lost. Further, since the SiC raw material is very expensive, the high-purity silicon carbide brick becomes very expensive as compared with the refractory bricks generally used.

【0004】このような高純度炭化珪素れんがの欠点を
解決するものとして、例えば特開昭62−283869号公報に
は、SiCを15〜70重量%、実質的に残部のSiO
2/Al23の重量成分比を1.5以上にしたことを特徴
とするSiC、SiO2、Al23を主成分とする燃焼
炉用耐火れんがが開示されている。
As a solution to such a drawback of high-purity silicon carbide bricks, for example, in JP-A-62-283869, 15 to 70% by weight of SiC and substantially the balance of SiO 2 are disclosed.
A refractory brick for a combustion furnace containing SiC, SiO 2 , or Al 2 O 3 as a main component, which has a weight component ratio of 2 / Al 2 O 3 of 1.5 or more is disclosed.

【0005】[0005]

【発明が解決しようとする課題】しかし、上述のような
SiO2−Al23系の珪酸塩結合を有する炭化珪素質
れんがは一般的に800〜1100℃までは水蒸気また
は酸素によるSiC酸化に伴う体積及び重量増加があ
り、早期損傷に至る。また、1100℃付近からSiC
酸化反応が顕著になり、SiCの焼失に伴う体積及び重
量減少が認められ、SiCれんがの特性を失うため炉の
実使用温度例えば1300℃では使用に耐え難くな
る。、また、溶融金属やアルカリを含む溶融焼却灰との
反応による損傷も大きくなる。これらの理由から炭化珪
素質れんが以外の材質例えば高アルミナ質れんがなどの
使用も試みられているが、ダスト、クリンカーの付着な
どにより操業に支障を招くことがある。
However, the above-mentioned silicon carbide brick having a SiO 2 -Al 2 O 3 type silicate bond is generally subjected to SiC oxidation by steam or oxygen up to 800 to 1100 ° C. There is an associated increase in volume and weight, leading to premature damage. Also, from around 1100 ° C, SiC
Oxidation reaction becomes remarkable, volume and weight decrease due to burning of SiC are recognized, and the characteristics of SiC brick are lost, so that it becomes difficult to withstand use at the actual operating temperature of the furnace, for example, 1300 ° C. In addition, the damage caused by the reaction with the molten incineration ash containing the molten metal and the alkali becomes large. For these reasons, the use of materials other than silicon carbide bricks, such as high alumina bricks, has been attempted, but dust or clinker adhesion may interfere with operation.

【0006】従って、本発明の目的は、近年の燃焼炉等
の使用条件の苛酷化例えばごみ燃焼炉ではごみ質の高カ
ロリー化のための高温燃焼による炭化珪素質れんがの耐
用性の低下を防止でき、また、焼却灰溶融炉では、14
00℃以上の高温域においても、耐食性、耐スポーリン
グ性、クリンカー難着性などの必要特性に優れ、これら
諸特性に優れ、耐用性を向上できる高耐食性炭化珪素・
アルミナ質れんがを提供することにある。
Therefore, the object of the present invention is to prevent the deterioration of the durability of silicon carbide bricks due to high temperature combustion in recent years in severe conditions of use of combustion furnaces, etc., for example, in a refuse combustion furnace to increase the calorie of the refuse quality. In addition, in the incinerator ash melting furnace,
Excellent corrosion resistance, spalling resistance, clinker adhesion resistance, and other required properties even at high temperatures above 00 ° C.
The purpose is to provide alumina bricks.

【0007】[0007]

【課題を解決するための手段】即ち、本発明に係る焼却
炉または焼却灰溶融炉用高耐食性炭化珪素・アルミナ質
れんがは、粒径5〜0.044mmのAl23含量99.
0%以上の高純度電融アルミナまたは焼結アルミナ20
〜60重量%、粒径0.03mm以下のAl23含量9
9.0%以上の高純度仮焼アルミナ5〜25重量%及び
粒径0.01mm以上の炭化珪素15〜60重量%を含
有してなる混合物に、Si、Al、B 4 C、ホウ砂、ホ
ウ酸を外掛で5重量%未満含有してなる配合物を成形
し、焼成して得られる見掛気孔率15%未満の成形体よ
りなることを特徴とする。
That is, the incineration according to the present invention
High corrosion resistance silicon carbide / alumina brick for furnace or incinerator ash melting furnace , Al 2 O 3 content 99.
0% or more of high-purity fused alumina or sintered alumina 20
~ 60 wt%, Al 2 O 3 content of particle size 0.03 mm or less 9
A mixture containing 5 to 25% by weight of high-purity calcined alumina of 9.0% or more and 15 to 60% by weight of silicon carbide having a particle size of 0.01 mm or more , Si, Al, B 4 C, borax, E
A molded product having an apparent porosity of less than 15%, which is obtained by molding a composition containing oxalic acid in an amount of less than 5% by weight and firing .
It is characterized by becoming

【0008】[0008]

【作用】本発明の高耐食性炭化珪素・アルミナ質れんが
には高純度電融アルミナまたは焼結アルミナを20〜6
0重量%配合する。これらの原料のAl23含量は9
9.0重量%以上であることが望ましく、また、粒径は
5〜0.044mmの範囲内のものが好ましい。なお、
上記配合量が20重量%未満では、耐食性が大幅に劣る
傾向にあり、炭化珪素の含量が増加すると、SiCの酸
化によりれんがの残存線膨張が大きくなるために好まし
くない。更に、上記配合量が60重量%を超えると弾性
率が高くなることから耐スポーリング性に劣ると同時に
炭化珪素の含量が減少するためクリンカー剥離性が劣る
傾向が認められるために好ましくない。また、粒径が上
記範囲外の場合には、れんがの組織が不良となり、成形
時のラミネーション(亀裂)や粗粒偏在及び焼成収縮の変
化が大きくれんが品質が劣るために好ましくない。
The high-corrosion silicon carbide / alumina brick of the present invention contains high purity fused alumina or sintered alumina in an amount of 20-6.
Add 0% by weight. The Al 2 O 3 content of these raw materials is 9
It is preferably 9.0% by weight or more, and the particle size is preferably in the range of 5 to 0.044 mm. In addition,
If the content is less than 20% by weight, the corrosion resistance tends to be significantly inferior, and if the content of silicon carbide increases, the residual linear expansion of the brick increases due to the oxidation of SiC, which is not preferable. Further, if the content is more than 60% by weight, the elastic modulus becomes high, so that the spalling resistance is inferior, and at the same time, the content of silicon carbide is reduced and the clinker peeling property tends to be inferior, which is not preferable. On the other hand, if the particle size is out of the above range, the structure of the brick becomes poor, lamination (cracks) at the time of molding, uneven distribution of coarse particles and change in firing shrinkage are large, and the quality of the brick is inferior, which is not preferable.

【0009】次に、本発明のれんがには、高純度仮焼ア
ルミナを5〜25重量%配合する。この仮焼アルミナを
配合することにより成形性が良好になり、また、焼成に
よって焼結が促進され、アルミナと炭化珪素を緻密に結
合させることができ、得られるれんがの気孔率及び通気
性を著しく低下させることができる。
Next, the brick of the present invention is compounded with 5 to 25% by weight of high-purity calcined alumina. By blending this calcined alumina, the formability becomes good, and the sintering is promoted by firing, so that alumina and silicon carbide can be closely bonded, and the porosity and air permeability of the resulting brick are remarkably increased. Can be lowered.

【0010】この仮焼アルミナのAl23含量も99.
0重量%以上のものが望ましい。また、高純度仮焼アル
ミナの粒径は0.03mm以下のものが望ましく、より
好ましくは0.004mm以下を主体とすることが、れ
んがの成形性と焼結性において好ましい。配合量が5重
量%未満では、成形性を付与することができず、また、
焼成によって緻密なれんが組織が得られない。また、2
5重量%を超えると成形時にラミネーションが発生し易
く、また、焼成収縮が大きく、緻密な組織が得られな
い。
The Al 2 O 3 content of this calcined alumina is also 99.
It is preferably 0% by weight or more. The particle size of the high-purity calcined alumina is preferably 0.03 mm or less, and more preferably 0.004 mm or less as the main component in terms of formability and sinterability of the brick. If the blending amount is less than 5% by weight, moldability cannot be imparted, and
The dense brick structure cannot be obtained by firing. Also, 2
If it exceeds 5% by weight, lamination tends to occur at the time of molding, firing shrinkage is large, and a dense structure cannot be obtained.

【0011】更に、本発明のれんがには、粒径0.01
mm以上の炭化珪素15〜60重量%配合する。配合量
が15重量%未満では、クリンカーの付着が多く、ま
た、耐スポーリング性に劣るなど炭化珪素の添加効果が
薄れるため好ましくない。また、60重量%を超えると
アルミナ含量が低くなり、耐食性に劣るために好ましく
ない。
Further, the brick of the present invention has a particle size of 0.01.
15 to 60% by weight of silicon carbide of mm or more is blended. If the blending amount is less than 15% by weight, the clinker is often attached and the effect of adding silicon carbide is deteriorated such as poor spalling resistance, which is not preferable. On the other hand, if it exceeds 60% by weight, the alumina content becomes low and the corrosion resistance becomes poor, which is not preferable.

【0012】炭化珪素は粒径が細かいほど表面積が大き
くなり、酸化反応を起こし易くなる。従って、粒径0.
01mm未満の炭化珪素を多く含むと耐酸化性に劣り、
れんが使用時に、れんが中のSiO2含量が増加し、耐
食性が低下する。また、れんが使用中の酸化による残存
線膨張が起こり易く好ましくない。
The smaller the particle size of silicon carbide, the larger the surface area of silicon carbide and the more likely it is to cause an oxidation reaction. Therefore, the particle size is 0.
If a large amount of silicon carbide of less than 01 mm is included, the oxidation resistance is poor,
When the brick is used, the content of SiO 2 in the brick increases and the corrosion resistance decreases. Further, residual linear expansion is likely to occur due to oxidation during use of brick, which is not preferable.

【0013】本発明のれんがには、上述の耐火原料より
なる混合物へ更に酸化防止及び熱間での強度付与の目的
で、Si、Al、B4C、ホウ砂、ホウ酸等を外掛で5
重量%未満の量で配合する
The brick of the present invention comprises the above-mentioned refractory raw materials .
For the purpose of further preventing oxidation and imparting strength to the resulting mixture , Si, Al, B 4 C, borax, boric acid, etc. are externally applied to the mixture.
It is blended in an amount of less than wt% .

【0014】また、本発明のれんが成形用配合物の調製
に当たっては、可塑性原料が少ないので、界面活性剤と
して例えばナフタレンスルホン酸ソーダ、ヘキサメタリ
ン酸ソーダ等が使用できる。また、有機可塑剤として例
えばCMC、PVA、糖蜜、パルプ廃液等を使用して成
形性を向上することもできる。
Further, in the preparation of the brick molding compound of the present invention, since there are few plastic raw materials, sodium naphthalene sulfonate, sodium hexametaphosphate, etc. can be used as the surfactant. Further, as the organic plasticizer, for example, CMC, PVA, molasses, pulp waste liquid or the like can be used to improve the moldability.

【0015】なお、成形に当たっては一軸加圧型プレス
で容易に成形することができるが、静水圧プレスを使用
することも可能である。
The molding can be easily carried out by a uniaxial pressure type press, but it is also possible to use a hydrostatic press.

【0016】本発明のれんがは上述のような配合物を所
定の形状に成形し、常法に従って1400〜1600℃
の温度範囲で焼成することにより得られる。
The brick of the present invention is prepared by molding the above-mentioned compound into a predetermined shape and then according to a conventional method, 1400 to 1600 ° C.
It is obtained by firing in the temperature range of.

【0017】また、得られたれんがは見掛気孔率が15
%未満であることが好ましい。見掛気孔率が15%を超
えると通気性が大きくなり、炉内ガス中の酸素がれんが
内部に侵透し易く、炭化珪素の一部は酸化し、れんが中
のSiO2含量が増加し、耐食性が低下するために好ま
しくない。なお、れんが中のSiO2含量は7重量%未
満とすることが好ましい。
The brick obtained has an apparent porosity of 15
It is preferably less than%. When the apparent porosity exceeds 15%, the air permeability becomes large, oxygen in the furnace gas easily penetrates into the inside of the brick, some of the silicon carbide is oxidized, and the SiO 2 content in the brick increases, It is not preferable because the corrosion resistance decreases. The SiO 2 content in the brick is preferably less than 7% by weight.

【0018】更に、本発明のれんがに、環境等の問題は
あるが、酸化クロム等のクロム原料を配合すれば耐食性
を大幅に向上することができる。
Further, although the brick of the present invention has a problem of environment and the like, the corrosion resistance can be greatly improved by incorporating a chromium raw material such as chromium oxide.

【0019】[0019]

【実施例】実施例1 以下の表1に示す配合割合にて配合物を作製し、成形及
び乾燥後、1530℃で焼成して本発明品及び比較品の
れんがを得た。得られたれんがの諸特性を表1に併記す
る。
EXAMPLES Example 1 Blends were prepared in the blending ratios shown in Table 1 below, molded, dried, and fired at 1530 ° C. to obtain bricks of the present invention and comparative products. Table 1 also shows various properties of the obtained brick.

【0020】[0020]

【表1】 [Table 1]

【0021】使用例1 従来、焼却炉燃焼部には、比較品E及びFのれんがが使
用されていたが、廃棄物の多様化、高カロリー化、使用
条件の苛酷化により溶融損傷、スポーリング、SiC酸
化膨大等により従来より耐用性が低下していた。焼却炉
燃焼部に本発明品Bを使用した結果、耐食性、耐酸化性
の向上により従来2年程度の耐用であっかのが、約4年
にれんが寿命を延長させることができた。
Use Example 1 Conventionally, goodwill of the comparative products E and F was used in the combustion section of the incinerator, but melt damage, spalling due to diversification of waste, increase in calorie, and severe usage conditions. , The durability was lower than in the past due to the excessive oxidation of SiC. As a result of using the product B of the present invention in the burning part of the incinerator, it was possible to extend the life of the bricks to about 4 years, although the durability was about 2 years, due to the improvement in corrosion resistance and oxidation resistance.

【0022】使用例2 実施例1の本発明品A、B及びCと、比較品のD、E、
F、G、ジルコニアれんが、MgO−Cr23れんがな
どの各種炉材を、ごみ焼却灰溶融炉にてテストした。そ
の結果、本発明品以外の炉材は耐食性及び熱スポーリン
グなどの損傷が多く問題であった。本発明品はSiCの
添加効果による熱スポーリング性とクリンカー難着性及
び耐浸潤性の効果があり、電融アルミナ添加による耐食
性の効果と相俟って極めて良好な結果が得られ、現在、
本発明品Bを実炉で継続して使用している。
USE EXAMPLE 2 Inventive products A, B and C of Example 1 and comparative products D, E,
F, G, zirconia bricks, various furnaces material such as MgO-Cr 2 O 3 brick were tested at waste incineration ash melting furnace. As a result, the furnace materials other than the product of the present invention had many problems such as corrosion resistance and damage such as heat spalling. The product of the present invention has the effect of heat spalling property due to the addition effect of SiC, the clinker adhesion resistance and the infiltration resistance, and in combination with the effect of the corrosion resistance due to the addition of fused alumina, an extremely good result is obtained, and at present,
The product B of the present invention is continuously used in an actual furnace.

【0023】[0023]

【発明の効果】本発明の高耐食性炭化珪素・アルミナ質
れんがは、低気孔率、低通気性を有するものであり、高
温域における酸素あるいは水蒸気などに対する耐酸化性
に優れている。また、外来成分に対する浸潤抑制に効果
的であり、溶損、反応が少ない。また、耐摩耗性に優
れ、低SiC含量にもかかわらずダストの難着性、クリ
ンカー剥離性に優れ、更に、低膨張性で高強度を有して
いるため、熱衝撃抵抗性も大きい。
The highly corrosive silicon carbide / alumina brick of the present invention has a low porosity and a low air permeability, and is excellent in oxidation resistance to oxygen or water vapor in a high temperature range. In addition, it is effective in suppressing the infiltration of foreign components, and has little erosion and reaction. Further, it is excellent in abrasion resistance, excellent in dust adhesion and clinker peeling property despite the low SiC content, and has low thermal expansion and high strength, so that it has high thermal shock resistance.

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 粒径5〜0.044mmのAl23含量
99.0%以上の高純度電融アルミナまたは焼結アルミ
ナ20〜60重量%、粒径0.03mm以下のAl23
含量99.0%以上の高純度仮焼アルミナ5〜25重量
%及び粒径0.01mm以上の炭化珪素15〜60重量
%を含有してなる混合物に、Si、Al、B 4 C、ホウ
砂、ホウ酸を外掛で5重量%未満含有してなる配合物を
成形し、焼成して得られる見掛気孔率15%未満の成形
体よりなることを特徴とする焼却炉または焼却灰溶融炉
高耐食性炭化珪素・アルミナ質れんが。
1. A particle size 5~0.044mm Al 2 O 3 content of 99.0% or more purity fused alumina or sintered alumina 20-60% by weight of a particle size 0.03mm following Al 2 O 3
A mixture containing 5 to 25% by weight of high-purity calcined alumina having a content of 99.0% or more and 15 to 60% by weight of silicon carbide having a particle size of 0.01 mm or more is added to Si, Al, B 4 C, and boro.
Molding with an apparent porosity of less than 15% obtained by molding a composition containing sand and boric acid in an amount of less than 5% by weight and firing.
Incinerator or incinerator ash melting furnace characterized by comprising a body
High corrosion resistance silicon carbide / alumina brick for use .
JP3271180A 1991-10-18 1991-10-18 High corrosion resistance silicon carbide / alumina brick Expired - Fee Related JPH0777981B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP3271180A JPH0777981B2 (en) 1991-10-18 1991-10-18 High corrosion resistance silicon carbide / alumina brick

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3271180A JPH0777981B2 (en) 1991-10-18 1991-10-18 High corrosion resistance silicon carbide / alumina brick

Publications (2)

Publication Number Publication Date
JPH05105507A JPH05105507A (en) 1993-04-27
JPH0777981B2 true JPH0777981B2 (en) 1995-08-23

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JP3271180A Expired - Fee Related JPH0777981B2 (en) 1991-10-18 1991-10-18 High corrosion resistance silicon carbide / alumina brick

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JP5080736B2 (en) * 2005-12-01 2012-11-21 日本碍子株式会社 Refractory manufacturing method and refractory obtained thereby
JP6472286B2 (en) * 2015-03-19 2019-02-20 東京窯業株式会社 Molten metal holding device

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FR2223330A1 (en) * 1973-03-28 1974-10-25 Norton Co Low temp firing alumina refractory body - comprises alumina, silicon carbide and opt. zirconia
JPS5425910A (en) * 1977-07-29 1979-02-27 Isolite Insulating Prod Antiispalling refractory

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