JPH08119731A - Zirconium dioxide fusion-cast refractory and production thereof - Google Patents
Zirconium dioxide fusion-cast refractory and production thereofInfo
- Publication number
- JPH08119731A JPH08119731A JP6234159A JP23415994A JPH08119731A JP H08119731 A JPH08119731 A JP H08119731A JP 6234159 A JP6234159 A JP 6234159A JP 23415994 A JP23415994 A JP 23415994A JP H08119731 A JPH08119731 A JP H08119731A
- Authority
- JP
- Japan
- Prior art keywords
- cao
- refractory
- zro
- ash
- cast refractory
- 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
Links
Landscapes
- Gasification And Melting Of Waste (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、一般廃棄物である都
市ごみ焼却灰や特別廃棄物としての飛灰（集塵灰）、感
染性廃棄物の焼却灰のような灰あるいは下水汚泥ケーキ
や産業廃棄物である鉄鋼業等から大量に排出される石炭
灰やスラグ等（以下廃棄物等という）のＣａＯの多いガ
ラスを溶融する際に適したＺｒＯ2 系溶融鋳造耐火物及
びその製造方法を提供するものである。BACKGROUND OF THE INVENTION The present invention relates to municipal waste incineration ash which is a general waste, fly ash (dust ash) as a special waste, ash such as incineration ash of infectious waste or sewage sludge cake, A ZrO 2 -based molten casting refractory suitable for melting glass containing a large amount of CaO such as coal ash and slag (hereinafter referred to as waste) that are discharged in large amounts from the steel industry, which is an industrial waste, and a method for producing the same. It is provided.
【０００２】[0002]
【従来の技術】ＺｒＯ2 ９０〜９５重量％，ＳｉＯ2
４〜６重量％，ＣａＯ ０．２重量％以下，Ａｌ2 Ｏ
3 ２重量％以下程度の従来の一般的なＺｒＯ2 質溶融
鋳造耐火物は、電気ガラスや光学ガラスのような通常の
ガラスを溶融する場合には耐蝕性のある耐火物として、
従来から広く使用されている。しかるに、このような一
般的なＺｒＯ2 質溶融鋳造耐火物をＣａＯ分の多いガラ
ス例えば最近注目を集めているごみ焼却場から出る焼却
灰や飛灰（集塵灰）等の廃棄物等のようなガラスを溶融
する炉の内張材に使用すると、ＺｒＯ2 質溶融鋳造耐火
物はそこに含まれているＣａＯにより激しく浸蝕されて
３ヶ月〜半年程度しか使用できない。ごみ焼却場から出
る焼却灰や飛灰は、そのままでは融点が高すぎて溶融し
にくいので、石灰石等のＣａＯ分を添加してその融点を
下げているのが実情であり、特に飛灰に関しては含有す
るＨｃｌ分を中和するために消石灰を噴霧しており、こ
の融点を下げるため及び中和のためのＣａＯの添加が同
時にガラス化を容易にするための融剤ともなっている
が、これが炉壁を痛める最大の原因となっていた。又、
特に鉄鋼業から大量に排出される石炭灰やスラグにもＣ
ａＯ分が多量に含まれており、同様にその溶融処理にお
いて、内張材に使用されるＺｒＯ2 質溶融鋳造耐火物が
浸蝕されるという問題があった。 2. Description of the Related Art ZrO 2 90 to 95% by weight, SiO 2
4-6 wt%, CaO 0.2 wt% or less, Al 2 O
3 2 wt% conventional general ZrO 2 quality fused cast refractory of the degree or less, as a refractory having resistance in the case of melting ordinary glass such as electrical glass and optical glass,
It has been widely used from the past. However, such a general ZrO 2 -based fused cast refractory is used as a glass containing a large amount of CaO, such as wastes such as incineration ash and fly ash (dust ash) from a refuse incinerator, which has been attracting attention recently. When used lining material of the furnace for melting a glass, allows only severely eroded by about 3 months to six months by CaO ZrO 2 quality fused cast refractories are contained therein. The incineration ash and fly ash from the refuse incinerator have a melting point that is too high and are difficult to melt as they are, so it is the reality that CaO content such as limestone is added to lower the melting point. Slaked lime is sprayed to neutralize the contained Hcl, and addition of CaO for lowering the melting point and neutralization also serves as a flux for facilitating vitrification. It was the biggest cause of hurt the wall. or,
Especially for coal ash and slag discharged in large quantities from the steel industry, C
There is a problem that a large amount of aO is contained, and similarly, in the melting treatment, the ZrO 2 -based fused cast refractory used for the lining material is corroded.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、例えばごみ
焼却場から出る焼却灰や飛灰のような廃棄物等のＣａＯ
分の多い成分のガラスを溶融する場合に耐蝕性のあるＺ
ｒＯ2 系溶融鋳造耐火物及びその製造方法を提供しよう
とするものである。DISCLOSURE OF INVENTION Problems to be Solved by the Invention The present invention is directed to CaO such as wastes such as incineration ash and fly ash from a refuse incinerator.
Corrosion resistant Z when melting glass with high content
It is intended to provide an rO 2 -based melt cast refractory material and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、ＺｒＯ2
系溶融鋳造耐火物がＣａＯによって浸蝕される状況を詳
細に観察検討することによって、以下に述べるような改
善策を見出したものである。The present inventors have found that ZrO 2
By observing and examining in detail the situation in which the system melt cast refractory is corroded by CaO, the following improvement measures have been found.
【０００５】[0005]
【作用】すなわち、浸蝕を受けたＺｒＯ2 質溶融鋳造耐
火物の表面層は、ジルコニア結晶粒部もマトリックス部
も比較的一様に浸蝕されているように見える。しかしな
がらこれをさらに詳細に観察すると、焼却灰や飛灰中の
ＣａＯが、耐火物中のジルコニア結晶に拡散して安定化
ジルコニア様の変質層が耐火物のガラス接触面に形成さ
れ、しかもこの安定化ジルコニア様の変質層が形成され
た部分は、それが形成されなかった部分より比較的浸蝕
を受けていないことが観察された。In other words, the surface layer of the ZrO 2 -based fused cast refractory that has been corroded appears to be relatively uniformly corroded in both the zirconia crystal grains and the matrix. However, when observing this in more detail, CaO in the incineration ash and fly ash diffuses into the zirconia crystals in the refractory, forming a stabilized zirconia-like alteration layer on the glass contact surface of the refractory, and It was observed that the portion where the altered layer like the zirconia-containing layer was formed was relatively less eroded than the portion where it was not formed.
【０００６】この安定化ジルコニアの変質層は、灰成分
が最も容易に侵入できるマトリックスガラスが非常に減
少しているため、溶融ガラスに対する一種の保護層にな
る。この保護層はわずかづつ浸蝕されていくが、その場
合でもより内部に新たな保護層が形成されるため、永続
的に形成され続けていくことになる。本発明者らは、こ
の現象を考察して、ＺｒＯ2 系溶融鋳造耐火物を鋳造す
る際に予めＣａＯを２重量％前後配合しておくことによ
って鋳造物が焼却灰や飛灰と接して熱影響を受けた時
に、その内部成分のみの働きにより安定化ジルコニア様
の変質層が形成されるようにしたものである。従って、
焼却灰や飛灰中の変動するＣａＯ含有量に左右されず、
安定化ジルコニア様の変質層を界面に常に形成すること
ができる。The modified layer of this stabilized zirconia is a kind of protective layer against molten glass because the matrix glass into which the ash component can most easily penetrate is greatly reduced. This protective layer is eroded little by little, but even in that case, a new protective layer is formed further inside, so that it continues to be formed permanently. In consideration of this phenomenon, the inventors of the present invention blended CaO in an amount of about 2% by weight in advance when casting a ZrO 2 -based melt-cast refractory, so that the cast was in contact with incinerated ash or fly ash and was heated. When affected, a stabilized zirconia-like altered layer is formed by the action of only the internal components. Therefore,
Not affected by the varying CaO content in incineration ash and fly ash,
A stabilized zirconia-like altered layer can always be formed at the interface.
【０００７】このＺｒＯ2 系溶融鋳造耐火物中のＣａＯ
は、主としてマトリックスガラス部に存在し、ＣａＯが
被溶融物から供給されないようなＣａＯ含有量の比較的
少ない汚泥ケーキや焼却灰と接している場合には安定化
ジルコニアを形成するためのＣａＯの供給源となる。耐
スポーリング性は幾分劣るようになっても、キャスタブ
ルの裏張りで補強する等の対策を講ずれば、通常のＣａ
Ｏ量のＺｒＯ2 質溶融鋳造耐火物と比較して使用不可能
な程のものではない。しかも、耐蝕性については熱影響
を受けて界面部分が安定化ジルコニア様の保護層に変質
するので、焼却灰や飛灰の中のＣａＯによってもほとん
ど浸蝕を受けず、従来のＺｒＯ2 質溶融鋳造耐火物と比
較して著しく優れている。この現象は、形成された安定
化ジルコニアが焼却灰や飛灰中のＣａＯによる侵蝕に対
して保護作用をしているものと推察される。CaO in this ZrO 2 type melt cast refractory
Is present mainly in the matrix glass part, and when it is in contact with sludge cake or incineration ash having a relatively low CaO content such that CaO is not supplied from the material to be melted, the supply of CaO for forming stabilized zirconia Be the source. Even if the spalling resistance is somewhat inferior, if you take measures such as reinforcing it with a castable lining, normal Ca
It is not as unusable as the O content of ZrO 2 fused cast refractories. Moreover, as for the corrosion resistance, the interface portion is transformed into a stabilized zirconia-like protective layer by being affected by heat, so it is hardly corroded by CaO in the incineration ash or fly ash, and the conventional ZrO 2 -based melt casting Remarkably superior to refractories. This phenomenon is presumed to be that the formed stabilized zirconia has a protective action against corrosion by CaO in incineration ash or fly ash.
【０００８】本発明はこの現象を利用してＺｒＯ2 質溶
融鋳造耐火物にあらかじめＣａＯを含有させて廃棄物等
のガラスと接したときにそこに含まれるＣａＯ含有量に
左右されずに耐火物中の内部成分の働きにより安定化ジ
ルコニアの保護層を作らせ、耐火物の耐蝕性を改善した
ものである。By utilizing this phenomenon, the present invention allows the refractory to contain CaO in advance in the ZrO 2 melt-casting refractory and is not affected by the CaO content contained in the refractory when it comes into contact with glass such as waste. The protective layer of stabilized zirconia is formed by the function of the internal components, and the corrosion resistance of refractory materials is improved.
【０００９】耐火物中のＣａＯを０．５〜７重量％に限
定したのは、これより少ないと安定化ジルコニアが形成
されないか極く僅かであるため効果が薄く、これより多
いと製造工程上クラックのない鋳塊が得られないためで
ある。The reason why the CaO content in the refractory material is limited to 0.5 to 7% by weight is that if the amount is less than this, stabilized zirconia is not formed or it is very small, and the effect is small. This is because an ingot without cracks cannot be obtained.
【００１０】[0010]
【実施例】以下に本発明の実施例について説明する。表
１に示したＺｒＯ2 系溶融鋳造耐火物の浸蝕テストを実
施した。EXAMPLES Examples of the present invention will be described below. The erosion test of the ZrO 2 system melt cast refractory shown in Table 1 was carried out.
【００１１】[0011]
【表１】 [Table 1]
【００１２】対象となるガラス（試験灰）の種類及び化
学組成を表２に示した。侵食テスト試料は約２０φ×８
０ｍｍの円柱試料で、内容積１８０×１８０×８０ｍｍ
の坩堝内に満たした試験灰の溶融ガラスにこれらのテス
ト試料を浸漬した。試験条件は１４５０℃で７２ｈｒで
ある。Table 2 shows the type and chemical composition of the target glass (test ash). Erosion test sample is about 20φ × 8
0 mm cylindrical sample, internal volume 180 x 180 x 80 mm
These test samples were immersed in a molten glass of test ash filled in the crucible. The test conditions are 1450 ° C. and 72 hours.
【００１３】[0013]
【表２】 [Table 2]
【００１４】表３に各種試験灰に対するテスト試料のガ
ラスライン浸蝕量（ｍｍ）を示した。Table 3 shows the glass line erosion amount (mm) of each test sample with respect to each test ash.
【００１５】[0015]
【表３】 [Table 3]
【００１６】実施例１〜６と比較例１〜４とを比較する
と、試験灰の種類を問わず同じＺｒＯ2 の含有量では実
施例が比較例よりもガラスライン浸蝕量が小さいといえ
る。従って、ＣａＯの添加効果によってＺｒＯ2 系溶融
鋳造耐火物の耐蝕性は向上していると考えられる。実施
例と比較例を同じＺｒＯ2 の含有量でその浸蝕量を比較
すると、平均で約１．５倍耐蝕性が向上している。Comparing Examples 1 to 6 with Comparative Examples 1 to 4, it can be said that the Example has a smaller glass line erosion amount than the Comparative Example at the same ZrO 2 content regardless of the type of test ash. Therefore, it is considered that the corrosion resistance of the ZrO 2 system melt cast refractory is improved by the addition effect of CaO. Comparing the amounts of corrosion with the same ZrO 2 content in the examples and the comparative examples, the corrosion resistance is improved about 1.5 times on average.
【００１７】[0017]
【発明の効果】本発明によるＺｒＯ2 系溶融鋳造耐火物
を焼却灰や飛灰等の廃棄物等の溶融炉の内張りに使用す
れば、耐火物の寿命を従来のＺｒＯ2 質溶融鋳造耐火物
よりも約１．５倍伸ばすことができる。The use of ZrO 2 based fused cast refractories according to the present invention, according to the present invention the lining of the melting furnace waste such as incineration ash and fly ash, the life of a conventional ZrO 2 quality fused cast refractories Refractories It can be extended about 1.5 times.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｆ２３Ｍ 5/00 Ｂ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display area F23M 5/00 B
Claims (2)
２〜１０重量％，ＣａＯ ０．５〜７重量％及びＡｌ2
Ｏ3 ４重量％以下を含有してなるＣａＯ含有ガラスに
耐蝕性のあるＺｒＯ2 系溶融鋳造耐火物1. ZrO 2 85% by weight or more, SiO 2
2-10 wt%, CaO 0.5-7 wt% and Al 2
ZrO 2 type melt-cast refractory having corrosion resistance to CaO-containing glass containing 4% by weight or less of O 3 .
上，ＳｉＯ2 ２〜１０重量％，ＣａＯ ０．５〜７重
量％及びＡｌ2 Ｏ3 ４重量％以下となるようにＺｒＯ
2 を主成分とする原料にＣａＯを添加して溶融鋳造し、
熱処理により安定化ジルコニアが形成されるようにした
ことを特徴とするＣａＯ含有ガラスに対して耐蝕性のあ
るＺｒＯ2 系溶融鋳造耐火物の製造方法2. The composition of the refractory is ZrO 2 85% by weight or more, SiO 2 2-10% by weight, CaO 0.5-7% by weight and Al 2 O 3 4% by weight or less.
CaO is added to the raw material containing 2 as the main component, and melt-casting is performed.
Stabilized zirconia is formed by heat treatment, and a method for producing a ZrO 2 -based melt-cast refractory having corrosion resistance to CaO-containing glass, characterized in that
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23415994A JP3278760B2 (en) | 1994-09-02 | 1994-09-02 | ZrO2-based molten cast refractories for melting furnaces such as incineration ash and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23415994A JP3278760B2 (en) | 1994-09-02 | 1994-09-02 | ZrO2-based molten cast refractories for melting furnaces such as incineration ash and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08119731A true JPH08119731A (en) | 1996-05-14 |
| JP3278760B2 JP3278760B2 (en) | 2002-04-30 |
Family
ID=16966586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23415994A Expired - Lifetime JP3278760B2 (en) | 1994-09-02 | 1994-09-02 | ZrO2-based molten cast refractories for melting furnaces such as incineration ash and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3278760B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015506898A (en) * | 2011-12-21 | 2015-03-05 | サン−ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン | Refractory products with high zirconia content |
-
1994
- 1994-09-02 JP JP23415994A patent/JP3278760B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015506898A (en) * | 2011-12-21 | 2015-03-05 | サン−ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン | Refractory products with high zirconia content |
| US9302943B2 (en) | 2011-12-21 | 2016-04-05 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Refractory product having a high content of zirconia |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3278760B2 (en) | 2002-04-30 |
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| EXPY | Cancellation because of completion of term |