JPH0596265A - Method for treating chromium containing refractory waste - Google Patents
Method for treating chromium containing refractory wasteInfo
- Publication number
- JPH0596265A JPH0596265A JP3282298A JP28229891A JPH0596265A JP H0596265 A JPH0596265 A JP H0596265A JP 3282298 A JP3282298 A JP 3282298A JP 28229891 A JP28229891 A JP 28229891A JP H0596265 A JPH0596265 A JP H0596265A
- Authority
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- Japan
- Prior art keywords
- chromium
- refractory
- waste material
- weight
- 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.)
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Processing Of Solid Wastes (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、製鋼プロセスやセメン
ト製造プロセスなどにおいて使用されるクロム含有耐火
物廃材の処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating chromium-containing refractory waste used in steel making processes, cement manufacturing processes and the like.
【０００２】[0002]
【従来の技術】クロム鉱を骨材として使用する、あるい
はさらに酸化クロムを添加しているクロム含有耐火物
は、特にはマグネシアクロム質耐火物は、スラグ、溶融
金属、溶融セメントクリンカー等に対して優れた耐食性
を有することから、製鋼プロセスや非鉄金属の冶金およ
びセメント製造プロセスのキーとなるプロセスにおいて
欠くことができない耐火物としてかなりの量が使用され
ている。2. Description of the Related Art Chromium-containing refractories using chrome ore as an aggregate or further adding chrome oxide, especially magnesia chrome refractories, are suitable for slag, molten metal, molten cement clinker, etc. Due to its excellent corrosion resistance, a considerable amount of refractory is used as an indispensable refractory in the key processes of steel making processes and metallurgy of non-ferrous metals and cement manufacturing processes.
【０００３】しかしながら、使用済みのクロム含有耐火
物廃材中には、数ppm と少量ではあるがクロム成分の一
部が６価のクロムとして含有されており、廃棄すると水
に溶け出す虞があることから、公害を防止する必要上廃
棄処理には厳しい制約が課せられている。However, although the used chromium-containing refractory waste material contains a small amount of several ppm, a part of the chromium component is contained as hexavalent chromium, which may dissolve into water when discarded. Therefore, strict restrictions are imposed on the disposal process because of the need to prevent pollution.
【０００４】このため、クロム含有耐火物廃材は粉砕し
て耐火物の原料としてできるだけ再使用するが、再使用
できないような不純物成分が混入したクロム含有耐火物
廃材は、製鋼用の原料として使用されるフェロクロムを
製造するプロセスと類似の電気溶融プロセスを適用し
て、クロム成分の大部分をフェロクロムとして回収する
とともに、残渣中の６価のクロム成分を還元し、水に溶
けない形態に変えた上で廃棄処理することが行われてい
る。Therefore, although the chromium-containing refractory waste material is crushed and reused as a raw material for the refractory material as much as possible, the chromium-containing refractory waste material mixed with impurities that cannot be reused is used as a raw material for steelmaking. In addition to recovering most of the chromium component as ferrochrome by applying an electric melting process similar to the process for producing ferrochrome, the hexavalent chromium component in the residue was converted into a form insoluble in water. Is being disposed of.
【０００５】しかしながら、この処理プロセスでは、回
収されて得られるフェロクロムの付加価値は、電気溶融
プロセスに要する費用を賄うのに必ずしも十分でなく、
さらに残渣の廃棄処理にも費用が必要であることから、
処理されない状態のクロム含有耐火物廃材が相当多量に
保管されているのが現状である。However, in this treatment process, the added value of ferrochrome recovered and obtained is not always sufficient to cover the cost required for the electromelting process,
Furthermore, since disposal of the residue also requires costs,
The present situation is that a large amount of untreated chromium-containing refractory waste materials are stored.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、前述のクロ
ム含有耐火物廃材の処理費用をさらに軽減することを目
的とするものであり、具体的には処理後の残渣を耐火物
の骨材原料として使用できるものに転化することによっ
て、残渣の廃棄処理を不要にするクロム含有耐火物廃材
の処理方法を提供しようとするものである。SUMMARY OF THE INVENTION The present invention is intended to further reduce the treatment cost of the above-mentioned chromium-containing refractory waste material, and more specifically, the residue after the treatment is treated as a refractory aggregate. An object of the present invention is to provide a method for treating a chromium-containing refractory waste material which makes it unnecessary to dispose of the residue by converting it into a material that can be used as a raw material.
【０００７】[0007]
【課題を解決するための手段】本発明は前述の課題を解
決すべくなされたものであり、本発明のクロム含有耐火
物廃材の処理方法は、クロム含有耐火物廃材に、クロム
鉱と、70重量％以上のアルミナ成分を含むアルミナ質原
料と、コークスとを混合し、黒鉛電極を用いる電気炉中
で溶融処理し、フェロクロムを回収するとともに、残渣
を大部分がスピネル結晶（AB2O4 においてA はFe、Mgな
ど、B はCr、Alなどからなる結晶）からなる固化体に転
化することを特徴とする。The present invention has been made to solve the above-mentioned problems, and a method for treating a chromium-containing refractory waste material of the present invention comprises: a chromium-containing refractory waste material; Alumina raw material containing more than wt% alumina component is mixed with coke, melted in an electric furnace using a graphite electrode to recover ferrochrome, and most of the residue is spinel crystal (AB 2 O 4 It is characterized in that A is converted to a solidified body composed of Fe, Mg, etc., and B is a crystal composed of Cr, Al, etc.).
【０００８】本発明のクロム含有耐火物廃材の処理方法
の好ましい態様では、アルミナ質原料中のシリカの含有
量が９重量％以下である。本発明のクロム含有耐火物廃
材の処理方法の他の好ましい態様では、クロム含有耐火
物廃材が５重量％以上のクロム成分を含むものである。
本発明のクロム含有耐火物廃材の処理方法の他の好まし
い態様では、前記固化体を破砕して耐火物の原料として
使用する。In a preferred embodiment of the method for treating a chromium-containing refractory waste material of the present invention, the content of silica in the alumina raw material is 9% by weight or less. In another preferred embodiment of the method for treating a chromium-containing refractory waste material of the present invention, the chromium-containing refractory waste material contains 5% by weight or more of a chromium component.
In another preferred aspect of the method for treating a chromium-containing refractory waste material of the present invention, the solidified body is crushed and used as a raw material for the refractory material.
【０００９】本発明のクロム含有耐火物廃材の処理方法
は、主としてマグネシアクロム質耐火物の廃材を処理し
てクロム成分をフェロクロムとして回収するとともに、
残渣を耐火物の骨材原料として使用できるように、耐火
度の高い骨材とするため、残渣の大部分をスピネル結晶
に転化させる。The method of treating a chromium-containing refractory waste material of the present invention mainly treats the waste material of magnesia chrome refractory material to recover the chromium component as ferrochrome,
Most of the residue is converted into spinel crystals so that the residue can be used as a raw material for a refractory aggregate so as to have high refractory aggregate.
【００１０】この場合、回収できるフェロクロムの量を
増やすためにクロム鉱を加え、残渣をスピネル結晶とす
るのに不足しているアルミナ成分をアルミナ質原料で補
給した上で電気溶融処理を行う。In this case, in order to increase the amount of ferrochrome that can be recovered, chrome ore is added, and the alumina component, which is insufficient to turn the residue into spinel crystals, is replenished with the aluminous raw material, and then the electric melting process is performed.
【００１１】コークスは還元剤であり、これらの混合物
を黒鉛電極を備えた電気炉中に投入して通電加熱し溶融
すると、コークスは酸化クロムを還元して金属クロムを
生成せしめる他、酸化鉄を還元して金属鉄にし、シリカ
を還元して金属シリコンを生成する。これらの還元生成
物は混合した溶融状態で電気炉の底に溜まるので、適宜
抜き取って固化させ、フェロクロムを得る。Coke is a reducing agent, and when a mixture of these is placed in an electric furnace equipped with a graphite electrode and heated by electric heating to melt, the coke reduces chromium oxide to produce metallic chromium, and also iron oxide. It is reduced to metallic iron and silica is reduced to produce metallic silicon. Since these reduced products are accumulated at the bottom of the electric furnace in a mixed and molten state, they are appropriately extracted and solidified to obtain ferrochrome.
【００１２】アルミナ質原料としては、残渣を低融点に
しないようにシリカ成分などの不純物が少なくてアルミ
ナ成分の多いもので、かつ安価なものを使用するのが好
ましい。具体的な例としては、ボーキサイトや礬土頁
岩、あるいはバイヤーアルミナなどを使用する。As the alumina-based raw material, it is preferable to use a low-melting raw material containing a small amount of impurities such as silica component and a large amount of alumina component so that the residue does not have a low melting point. As a specific example, bauxite, gravel shale, or Bayer alumina is used.
【００１３】天然原料中には多くの場合シリカ成分が含
まれており、シリカ成分が残渣中に多く残ると残渣の耐
火度が下がるので、好ましくはシリカ成分が９重量％以
下のアルミナ質原料を使用する。混合物中のシリカ成分
は、還元されてフェロクロム中に吸収される他、高温で
はSiO 蒸気となって揮散して減少するが、そのためには
相当量のエネルギーが消費されるので、始めからできる
だけ少なくなるようにアルミナ質原料を選ぶのが好まし
い。The natural raw material often contains a silica component, and if a large amount of the silica component remains in the residue, the fire resistance of the residue is lowered. Therefore, it is preferable to use an alumina-based raw material containing 9% by weight or less of the silica component. use. The silica component in the mixture is reduced and absorbed in ferrochrome, and at high temperatures it becomes SiO vapor and volatilizes and decreases, but this consumes a considerable amount of energy, so it is as small as possible from the beginning. Thus, it is preferable to select an alumina-based raw material.
【００１４】クロム鉱の化学組成は産地によって変化す
る他、クロム含有耐火物廃材中のマグネシア、酸化クロ
ムその他の含有量も品種と使用箇所によって変化するの
で、アルミナ質原料の混合量はこれらの点を考慮し、ス
ピネル組成の固化体が得られるように調整する。Since the chemical composition of chrome ore varies depending on the place of production, and the content of magnesia, chromium oxide, etc. in the refractory waste material containing chromium also varies depending on the variety and the place of use, the mixing amount of the aluminous raw material is these points. In consideration of the above, adjustment is performed so as to obtain a solidified body having a spinel composition.
【００１５】クロム含有耐火物廃材の処理は、あまりに
クロムの含有量の少ない耐火物廃材に適用しても有利で
はないので、好ましくは２重量％以上のクロム成分を含
む耐火物廃材に適用するのが好ましい。混合物の溶融処
理を行ってフェロクロムを抜き取り、その後電気炉中に
溜っている酸化物の溶融物は電気炉中でそのまま固化、
あるいは電気炉を傾けて取り出し、放冷して固化せしめ
る。Since the treatment of the refractory waste material containing chromium is not advantageous when applied to the refractory waste material containing too little chromium, it is preferably applied to the refractory waste material containing 2% by weight or more of the chromium component. Is preferred. The mixture is melted to remove ferrochrome, and then the oxide melt accumulated in the electric furnace is solidified as it is in the electric furnace.
Alternatively, the electric furnace is tilted and taken out, and allowed to cool and solidify.
【００１６】この固化体はスピネル結晶を主成分とする
ものであって、耐火度もあるので、破砕すれば耐火物の
原料として使用することができ、残渣を耐火物として有
効に利用することによって、残渣の廃棄処理を不要とす
ることができる。Since this solidified body contains spinel crystals as a main component and also has a refractory degree, it can be used as a raw material of a refractory material by crushing it, and by effectively utilizing the residue as a refractory material. Therefore, it is possible to eliminate the waste disposal of the residue.
【００１７】[0017]
【実施例】以下、本発明を実施例によって具体的に説明
するが、本発明はこれらの実施例によってなんら限定さ
れるものではない。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
【００１８】マグネシアクロム質耐火物の廃材で、MgO
73重量％、Al2O3 7 重量％、酸化クロムをCr2O3 換算で
11重量％、SiO2を２重量％および酸化鉄をFeO 換算で 5
重量％含むもの２部に対し、クロム鉱（MgO 21重量％、
Al2O3 27重量％、酸化クロムをCr2O3 換算で33重量％、
および酸化鉄をFeO 換算で15重量％およびSiO2を６重量
％含むもの）を８部と、Al2O3 成分を85重量％とSiO2を
７重量％含む礬土頁岩１部とコークス１部とを混合し、
合計600 kgの混合物を３本の黒鉛電極を備えた最大出力
100kVAの電気炉に投入し、電気溶融処理を行って約100k
gのフェロクロムを電気炉の底から抜き取った。次に電
気炉を傾けて、残りの溶融物の約半分を耐火物で内張り
した容器に移し、そのまま放冷した。Magnesia chrome refractory waste material, MgO
73% by weight, Al 2 O 3 7% by weight, chromium oxide in terms of Cr 2 O 3
11% by weight, 2 % by weight of SiO 2 and 5% of iron oxide in terms of FeO
Chromite (21% by weight of MgO,
Al 2 O 3 27% by weight, chromium oxide 33% by weight in terms of Cr 2 O 3 ,
And 15 parts by weight of iron oxide in terms of FeO and 6 parts by weight of SiO 2 ), 8 parts by weight, 85 parts by weight of Al 2 O 3 component and 1 part of conglomerate shale containing 7% by weight of SiO 2 and coke 1 And mix
Maximum output with three graphite electrodes for a total of 600 kg of mixture
It is put into an electric furnace of 100 kVA and the electric melting process is performed to about 100 k
g of ferrochrome was withdrawn from the bottom of the electric furnace. Next, the electric furnace was tilted, and about half of the remaining melt was transferred to a container lined with a refractory and allowed to cool.
【００１９】容器中で固化した固化体を調べたところ、
MgO 45重量％、Al2O3 45重量％、SiO28.5 重量％、Cr2O
3 1.2 重量％およびFeO 0.3 重量％からなり、大部分が
スピネル結晶であることが分かった。When the solidified body solidified in the container was examined,
MgO 45% by weight, Al 2 O 3 45% by weight, SiO 2 8.5% by weight, Cr 2 O
It consisted of 3 1.2 wt% and FeO 0.3 wt% and was found to be mostly spinel crystals.
【００２０】また、得られたフェロクロムの組成は、炭
素５重量％、Si３重量％、Fe32重量％、Cr60重量％であ
った。また、クロム含有耐火物廃材中の６価のクロムの
量をJIS に規定された溶出試験方法で調べたところ約５
ppm であったのに対し、固化体については検出すること
ができず、廃棄処理上問題がない0.05ppm 以下であるこ
とが確認された。The composition of the obtained ferrochrome was 5% by weight of carbon, 3% by weight of Si, 32% by weight of Fe and 60% by weight of Cr. In addition, when the amount of hexavalent chromium in the refractory waste material containing chromium was examined by the dissolution test method specified in JIS, it was about 5
Although it was ppm, it was confirmed that the solidified substance could not be detected, and it was 0.05 ppm or less, which is not a problem in waste treatment.
【００２１】次に、固化体を砕いて１mm以下の骨材と
し、耐火物の原料として使用し、得られた耐火物の性質
を調べた。すなわち、表１に示した調合のスピネルを含
有する耐火物を試作してその性質を調べ、代替可能と思
われる従来の耐火物の性質と比較した結果を同じ表１に
示した。Next, the solidified body was crushed into an aggregate of 1 mm or less, which was used as a raw material for the refractory, and the properties of the obtained refractory were investigated. That is, a refractory material containing the spinel having the formulation shown in Table 1 was experimentally manufactured and its properties were examined, and the results of comparison with the properties of conventional refractory materials which are considered to be replaceable are shown in the same Table 1.
【００２２】結合剤には、アルミナセメントの他、少量
のピロりん酸ソーダを解膠剤として加え、それぞれの調
合について適当量の水とともに万能ミキサー中で混合
し、鋳型中に振動を加えながら流し込み、40mm×40mm×
160mm の試験片を作製した。In addition to alumina cement, a small amount of sodium pyrophosphate was added as a deflocculant to the binder, and each formulation was mixed with an appropriate amount of water in a universal mixer and poured into a mold while vibrating. , 40mm x 40mm x
A 160 mm test piece was prepared.
【００２３】得られた試験片を110 ℃で24時間乾燥後、
それぞれについて嵩比重、見掛気孔率、圧縮強度、曲げ
強度を測定して、表１に併せて示した。また、表１に併
せて示した耐食性指数は、回転式侵食試験炉によって耐
火物を試験した結果である。After drying the obtained test piece at 110 ° C. for 24 hours,
The bulk specific gravity, apparent porosity, compressive strength, and bending strength were measured for each, and are also shown in Table 1. In addition, the corrosion resistance index also shown in Table 1 is the result of testing the refractory in a rotary erosion test furnace.
【００２４】すなわち、前記試験片を６個合わせてスタ
ンプ材を間に充填し、円筒状に組んで縁付きのルツボを
構成し、ルツボを横向きに配置した中に、CaO 54.8重量
％、Al2O3 28.5重量％、SiO28.6 重量％、MgO 7.1 重量
％およびFeO 1.0 重量％の組成からなる塩基性スラグ0.
6kg と同重量のSS41鋼片を合わせて入れ、ガスバーナで
加熱してスラグと鋼片を溶かし、ルツボを６RPM で回転
しながら1650℃に６時間保持して耐火物を侵食せしめ
た。That is, six test pieces were put together, filled with a stamp material, and assembled into a cylindrical shape to form a crucible with an edge. The crucible was arranged laterally, and CaO was 54.8 wt% and Al 2 O was added. 3 Basic slag consisting of 28.5% by weight, SiO 2 8.6% by weight, MgO 7.1% by weight and FeO 1.0% by weight.
6 kg of SS41 steel slab with the same weight was put together, heated with a gas burner to melt the slag and steel slab, and the crucible was kept at 1650 ° C for 6 hours while rotating at 6 RPM to erode the refractory.
【００２５】耐食性指数は、侵食された試験片の最大侵
食深さを試験片の試験前の厚さと試験後の厚さとの差か
ら求め、試験No.4の耐火物の最大侵食深さをC4とし、他
の試験耐火物の最大侵食深さをCnとして、耐食性指数＝
C4/Cn ×100 により求めたものである。The corrosion resistance index is obtained by determining the maximum erosion depth of the eroded test piece from the difference between the thickness of the test piece before the test and the thickness after the test, and the maximum erosion depth of the refractory of Test No. 4 is C 4 and the maximum corrosion depth of other test refractories as C n , the corrosion resistance index =
It is obtained by C 4 / C n × 100.
【００２６】[0026]
【表１】 [Table 1]
【００２７】以上の試験の結果から、耐火物廃材から得
られた固化体スピネルの骨材を使用し、現在使用されて
いる耐火物原料である電融スピネル（MgAl2O4 ）骨材と
置き換え、物性的にも耐食性の点でも十分使用できるレ
ベルの耐火物が得られることを確かめた。From the results of the above tests, the solidified spinel aggregate obtained from the refractory waste material was used and replaced with the electromelting spinel (MgAl 2 O 4 ) aggregate which is the currently used refractory raw material. It was confirmed that a refractory of a level that could be used in terms of physical properties and corrosion resistance was obtained.
【００２８】[0028]
【発明の効果】本発明のクロム含有耐火物廃材の処理方
法により、フェロクロムとして耐火物廃材中のクロムを
同時に回収し、かつ残渣を耐火物原料として使用できる
ものに転化することによって、クロム含有耐火物廃材の
処理コストを大幅に低減できると同時に、残渣の廃棄処
理を不要とすることができる。EFFECT OF THE INVENTION According to the method for treating a chromium-containing refractory waste material of the present invention, chromium in the refractory waste material is simultaneously recovered as ferrochrome, and the residue is converted into a material that can be used as a refractory raw material to obtain a chromium-containing refractory material. It is possible to significantly reduce the processing cost of waste materials, and at the same time, to eliminate the need for waste disposal processing.
Claims (4)
重量％以上のアルミナ成分を含むアルミナ質原料と、コ
ークスとを混合し、黒鉛電極を用いる電気炉中で溶融処
理し、フェロクロムを回収するとともに、残渣を大部分
がスピネル結晶からなる固化体に転化することを特徴と
するクロム含有耐火物廃材の処理方法。1. A chromium-containing refractory waste material containing chrome ore and 70
Alumina raw material containing more than wt% alumina component is mixed with coke, melted in an electric furnace using a graphite electrode to recover ferrochrome, and the residue is converted into a solidified body mainly composed of spinel crystals. A method for treating waste material of refractory material containing chromium, which comprises:
リカの含有量が９重量％以下であるクロム含有耐火物廃
材の処理方法。2. The method for treating a chromium-containing refractory waste material according to claim 1, wherein the silica content in the alumina raw material is 9% by weight or less.
火物廃材が２重量％以上のクロム成分を含むものである
クロム含有耐火物廃材の処理方法。3. The method for treating a chromium-containing refractory waste material according to claim 1 or 2, wherein the chromium-containing refractory waste material contains 2% by weight or more of a chromium component.
記固化体を破砕して耐火物の原料とするクロム含有耐火
物廃材の処理方法。4. The method for treating a chromium-containing refractory waste material according to claim 1, wherein the solidified body is crushed to be a refractory raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3282298A JPH0596265A (en) | 1991-10-02 | 1991-10-02 | Method for treating chromium containing refractory waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3282298A JPH0596265A (en) | 1991-10-02 | 1991-10-02 | Method for treating chromium containing refractory waste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0596265A true JPH0596265A (en) | 1993-04-20 |
Family
ID=17650604
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3282298A Withdrawn JPH0596265A (en) | 1991-10-02 | 1991-10-02 | Method for treating chromium containing refractory waste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0596265A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002263606A (en) * | 2001-03-05 | 2002-09-17 | Nippon Steel Corp | Treatment process of used refractory material |
| KR100426720B1 (en) * | 1998-12-29 | 2004-06-18 | 주식회사 포스코 | Tund Nozzle Protective Castable |
| WO2009072627A1 (en) | 2007-12-06 | 2009-06-11 | Agc Ceramics Co., Ltd. | Process for production of refractory particles |
-
1991
- 1991-10-02 JP JP3282298A patent/JPH0596265A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100426720B1 (en) * | 1998-12-29 | 2004-06-18 | 주식회사 포스코 | Tund Nozzle Protective Castable |
| JP2002263606A (en) * | 2001-03-05 | 2002-09-17 | Nippon Steel Corp | Treatment process of used refractory material |
| JP4499940B2 (en) * | 2001-03-05 | 2010-07-14 | 新日本製鐵株式会社 | Disposal of used refractories |
| WO2009072627A1 (en) | 2007-12-06 | 2009-06-11 | Agc Ceramics Co., Ltd. | Process for production of refractory particles |
| US8025824B2 (en) | 2007-12-06 | 2011-09-27 | Agc Ceramics Co., Ltd. | Process for producing refractory particles |
| JP5706615B2 (en) * | 2007-12-06 | 2015-04-22 | Ａｇｃセラミックス株式会社 | Method for producing refractory particles |
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