JP2003226571A - Method for manufacturing calcium aluminate containing oxygen radical - Google Patents
Method for manufacturing calcium aluminate containing oxygen radicalInfo
- Publication number
- JP2003226571A JP2003226571A JP2002030742A JP2002030742A JP2003226571A JP 2003226571 A JP2003226571 A JP 2003226571A JP 2002030742 A JP2002030742 A JP 2002030742A JP 2002030742 A JP2002030742 A JP 2002030742A JP 2003226571 A JP2003226571 A JP 2003226571A
- Authority
- JP
- Japan
- Prior art keywords
- calcium aluminate
- mass
- powder
- raw material
- oxygen
- 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
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、酸化触媒、イオン
伝導体等の用途展開が期待されている、活性酸素種であ
るＯ2 -やＯ-の酸素ラジカルを高濃度に含むカルシウム
アルミネートの製造方法に関する。また、本発明は、前
記製造方法で得られ粉末と、前記粉末から得られる緻密
で気体通過性のない焼結体に関する。TECHNICAL FIELD The present invention relates to a calcium aluminate containing a high concentration of oxygen radicals of O 2 − and O − which are active oxygen species, which are expected to be used for applications such as oxidation catalysts and ionic conductors. Manufacturing method The present invention also relates to the powder obtained by the above-mentioned manufacturing method, and a dense, gas-impermeable sinter obtained from the powder.
【０００２】[0002]
【従来の技術】Ｏ2 -やＯ-の酸素ラジカルは、活性酸素
の１種であり、有機物や無機物の酸化過程で重要な役割
を果たすことが知られている。酸化物化合物の固体表面
上に吸着したＯ2 -については、広範な研究が行われてい
る（Ｊ．Ｈ．Ｌｕｎｓｆｏｒｄ、Ｃａｔａｌ．Ｒｅｖ．
８，１３５，１９７３，Ｍ．Ｃｈｅ ａｎｄＡ．Ｊ．Ｔ
ｅｎｃｈ，Ａｄｖ．Ｃａｔａｌ，３２，１，１９８
３）。これらの研究のほとんどは、γ線などの高エネル
ギーの放射線を酸化物化合物表面に照射することでＯ2 -
を作成している。2. Description of the Related Art O 2 − and O − oxygen radicals are a type of active oxygen and are known to play an important role in the oxidation process of organic substances and inorganic substances. Extensive research has been conducted on O 2 − adsorbed on the solid surface of oxide compounds (JH Lunsford, Catal. Rev.
8,135,1973, M. Che and A. J. T
ench, Adv. Catal, 32, 1, 198
3). Most of these studies, O 2 by irradiating high-energy radiation such as γ rays oxide compound surface -
Are being created.
【０００３】Ｏ2 -を構成アニオンとする結晶はＲＯ
2（Ｒ＝アルカリ金属）が知れれているが、これらの化
合物はいずれも３００℃以下の低温で容易に分解してし
まうため、酸化触媒、イオン伝導体などの用途には使用
できない。Crystals having O 2 − as a constituent anion are RO
2 (R = alkali metal) is known, but all of these compounds are easily decomposed at a low temperature of 300 ° C. or lower, and therefore cannot be used for applications such as oxidation catalysts and ionic conductors.
【０００４】１９７０年にＨ．Ｂ．Ｂａｒｔｌらは、１
２ＣａＯ・７Ａｌ2Ｏ3（以下、Ｃ12Ａ7という）結晶に
おいては、２分子を含む単位胞にある６６個の酸素のう
ち、２個はネットワークに含まれず、結晶の中に存在す
るケージ内の空間に「フリー酸素」として存在すると主
張している（Ｈ．Ｂ．Ｂａｒｔｌ ａｎｄ Ｔ．Ｓｃｈ
ｅｌｌｅｒ、Ｎｅｕｅｓ Ｊａｒｈｒｂ．Ｍｉｎｅｒａ
ｌ．，Ｍｏｎａｔｓｈ．１９７０、５４７）。In 1970, H.M. B. Bartl et al.
In the 2CaO · 7Al 2 O 3 (hereinafter referred to as C 12 A 7 ) crystal, of the 66 oxygens in the unit cell containing 2 molecules, 2 are not included in the network, and are in the cage that exists in the crystal. It is claimed to exist as "free oxygen" in the space of H.B. (B. Bartl and T. Sch.
eller, Neues Jarhrb. Minera
l. Monatsh. 1970, 547).
【０００５】細野らは、ＣａＣＯ3とＡｌ2Ｏ3またはＡ
ｌ（ＯＨ）3を原料として空気中で１２００℃の温度で
固相反応により合成したＣ12Ａ7結晶中に１×１０19ｃ
ｍ-3程度のＯ2 -が包接されていることを電子スピン共鳴
の測定から発見し、フリー酸素の一部がＯ2 -の形でゲー
ジ内に存在するというモデルを提案している（Ｈ．Ｈｏ
ｓｏｎｏ ａｎｄ Ｙ．Ａｂｅ，Ｉｎｏｒｇ．Ｃｈｅ
ｍ．２６、１１９３、１９９７）。Hosono et al. Have reported that CaCO 3 and Al 2 O 3 or A
1 × 10 19 c in a C 12 A 7 crystal synthesized by solid-phase reaction in the air at a temperature of 1200 ° C. using 1 (OH) 3 as a raw material.
It was discovered from the measurement of electron spin resonance that O 2 − of about m −3 was included, and a model was proposed in which a part of free oxygen exists in the gauge in the form of O 2 − ( H. Ho
sono and Y. Abe, Inorg. Che
m. 26, 1193, 1997).
【０００６】このＣ12Ａ7は、融点１４１５℃の安定な
酸化物であり、包接されるＯ2 -の量が１０20ｃｍ-3以上
で比表面積が大きい粉末状の形態にできれば酸化触媒、
抗菌剤などとしての用途が開けるものと期待されてい
る。This C 12 A 7 is a stable oxide having a melting point of 1415 ° C., and if the amount of O 2 − to be clathrated is 10 20 cm −3 or more and the powder has a large specific surface area, it is an oxidation catalyst. ,
It is expected to be used as an antibacterial agent.
【０００７】細野らは、更に、前記Ｏ2 -を包接するＣ12
Ａ7について検討を行い、ＣａＣＯ3、Ｃａ（ＯＨ）2又
はＣａＯと、Ａｌ2Ｏ3又はＡｌ（ＯＨ）3とを原料に用
い、酸素分圧１０4Ｐａ以上、水蒸気分圧１０2Ｐａ以下
の乾燥酸化雰囲気下、１２００℃以上１４１５℃未満に
焼成し、固相反応させることで、活性酸素種であるＯ2 -
及びＯーを１０20ｃｍ-3以上の高濃度で包接するＣ12Ａ
7を得ている（特開２００２−３２１８公報参照）。Hosono et al. Further describe C 12 which includes the O 2 −.
Performs studied A 7, CaCO 3, Ca and (OH) 2 or CaO, using the Al 2 O 3 or Al (OH) 3 as a raw material, the oxygen partial pressure 10 4 Pa or more, less water vapor partial pressure 10 2 Pa under a dry oxidizing atmosphere, and fired in 1415 below ° C. 1200 ° C. or higher, by a solid phase reaction, O 2 is active oxygen species -
And O - containing C 12 A at a high concentration of 10 20 cm -3 or more
7 is obtained (see JP 2002-3218 A).
【０００８】[0008]
【発明が解決しようとする課題】しかし、細野らの見い
だした高濃度に活性酸素種を含有するＣ12Ａ7を産業上
利用する場合、更に解決するべき課題がある。However, when C 12 A 7 containing active oxygen species at a high concentration found by Hosono et al. Is industrially used, there is a problem to be further solved.
【０００９】即ち、高濃度の酸素ラジカルを含有するＣ
12Ａ7を酸化触媒、抗菌剤用途に適用する場合、当該用
途に応じた機能を充分発揮させる為には、それぞれの用
途にあった様々な形状（粉末状、粒状、塊状、板状、環
状、管状等）とする必要がある。That is, C containing a high concentration of oxygen radicals
When 12 A 7 is applied to an oxidation catalyst or an antibacterial agent, various shapes (powder, granules, lumps, plates, rings, etc.) suitable for each application are required in order to fully exhibit the function according to the use. , Tubular, etc.).
【００１０】つまり、高酸素ラジカル濃度のＣ12Ａ7を
含有するカルシウムアルミネートを、例えば、燃料電池
用隔壁等に用いる場合、ガス通過性が低くしかも酸素ラ
ジカルを輸送し得るように、緻密な成形体として得よう
とするときには、前記焼結過程での大きな寸法収縮のた
めに所望寸法のカルシウムアルミネート焼結体が得難い
という問題がある。That is, when calcium aluminate containing C 12 A 7 having a high oxygen radical concentration is used for, for example, a partition for a fuel cell, it has a low gas permeability and is dense so that oxygen radicals can be transported. When trying to obtain a compact, there is a problem that it is difficult to obtain a calcium aluminate sintered body having a desired size due to a large size shrinkage in the sintering process.
【００１１】Ｃ12Ａ7の如く無機物質を所望の形状とす
るためには、当該無機物質の粉末を用いプレス成形、押
出し成形、射出成形等の方法で形状を与え、その後焼成
・焼結することで当該用途において要求される程度にま
で強度等の特性を付与することが一般的である。このた
め、高濃度の酸素ラジカルを含有するＣ12Ａ7を粉末状
態で得ることは産業上非常に重要である。尚、粉末の程
度については一般に２ｍ2／ｇ以上の比表面積を有すれ
ば良い。In order to form an inorganic substance such as C 12 A 7 into a desired shape, powder of the inorganic substance is used to give a shape by a method such as press molding, extrusion molding, injection molding, and then firing and sintering. Therefore, it is common to impart properties such as strength to the extent required for the application. Therefore, it is very important industrially to obtain C 12 A 7 containing a high concentration of oxygen radicals in a powder state. Incidentally, regarding the degree of powder, it is generally sufficient that the powder has a specific surface area of 2 m 2 / g or more.
【００１２】しかし、粉末状態の高酸素ラジカル濃度の
Ｃ12Ａ7を得る方法として、予め２ｍ2／ｇ以上の比表面
積を有する粉末を原料とする方法も考えられるが、この
場合にはＣ12Ａ7が生成、結晶化する過程において焼結
してしまい、結果的に比表面積が２ｍ2／ｇ未満の荒い
粒子或いは塊となってしまう。However, as a method for obtaining C 12 A 7 having a high oxygen radical concentration in a powder state, a method using a powder having a specific surface area of 2 m 2 / g or more in advance as a raw material can be considered. In this case, C 12 A 7 is sintered in the process of being generated and crystallized, and as a result, it becomes coarse particles or agglomerates having a specific surface area of less than 2 m 2 / g.
【００１３】更に、他の課題として、細野らは原料に高
純度のカルシウム源、アルミニウム源を用いており、得
られる高酸素ラジカル濃度のＣ12Ａ7が高価とならざる
を得ず、産業レベルでの普及の上で大きな障害となる。Furthermore, as another problem, Hosono et al. Uses a high-purity calcium source and an aluminum source as raw materials, and the resulting high oxygen radical concentration C 12 A 7 is inevitably expensive. Will be a major obstacle to its spread.
【００１４】本発明者は、前記課題を解決するべく実験
的検討を重ねた結果、原料に基本的にＣ12Ａ7組成で非
晶質のカルシウムアルミネートを用いることで、或いは
Ｆｅ、Ｓｉ、Ｔｉ、Ｋのいずれか１種以上の存在下で所
定の条件を選択するときに、安価な原料を用いて前記高
酸素ラジカル濃度のＣ12Ａ7を含有するカルシウムアル
ミネートを得ることができ、例えば、有機物質を含有す
る自動車の排ガス用の酸化触媒等の用途に好適であると
いう知見を得て、本発明に至ったものである。又、前記
Ｃ12Ａ7を含有するカルシウムアルミネートの粉末を用
いるとき、高密度で気体通過性を有しない成形体が安定
して得られるという知見を得て、本発明に至ったもので
ある。The present inventor has conducted experimental studies to solve the above-mentioned problems, and as a result, by using amorphous calcium aluminate having a C 12 A 7 composition as a raw material, or Fe, Si, When selecting a predetermined condition in the presence of one or more of Ti and K, it is possible to obtain the calcium aluminate containing C 12 A 7 with a high oxygen radical concentration by using an inexpensive raw material, For example, the inventors of the present invention have arrived at the present invention by finding that they are suitable for applications such as oxidation catalysts for exhaust gas of automobiles containing organic substances. Further, when the powder of calcium aluminate containing C 12 A 7 is used, it was found that a compact having a high density and no gas permeability can be stably obtained, which led to the present invention. .
【００１５】[0015]
【課題を解決するための手段】本発明は、カルシウム
（Ｃａ）とアルミニウム（Ａｌ）をモル比で１１．８：
７．２〜１２．２：６．８含有し、しかも非晶質のカル
シウムアルミネートを原料に用い、前記原料を酸素分圧
４×１０4Ｐａ以上の雰囲気下１１００℃以上溶融温度
以下に加熱することで、当該カルシウムアルミネート中
に１２ＣａＯ・７Ａｌ2Ｏ3（以下、Ｃ12Ａ7という）を
形成し、しかも前記Ｃ12Ａ7が酸素ラジカルを１０20ｃ
ｍ-3以上含有させることを特徴とするカルシウムアルミ
ネートの製造方法である。According to the present invention, calcium (Ca) and aluminum (Al) have a molar ratio of 11.8:
Amorphous calcium aluminate containing 7.2 to 12.2: 6.8 is used as a raw material, and the raw material is heated to 1100 ° C. or higher and a melting temperature or lower in an atmosphere having an oxygen partial pressure of 4 × 10 4 Pa or higher. it is to, 12CaO · 7Al 2 O 3 in the calcium aluminate (hereinafter, C 12 a 7 hereinafter) is formed, yet the C 12 a 7 is 10 20 c oxygen radicals
A method for producing calcium aluminate characterized by containing m -3 or more.
【００１６】また、本発明は、ＣａとＡｌをモル比で１
１．８：７．２〜１２．２：６．８含有し、しかもＦ
ｅ、Ｓｉ、Ｔｉ、Ｋのいずれか１種以上が含有された原
料を、酸素分圧４×１０4Ｐａ以上の雰囲気下１１００
℃以上溶融温度以下に加熱することで、酸素ラジカルを
１０20ｃｍ-3以上のＣ12Ａ7を含有するカルシウムアル
ミネートを形成させることを特徴とするカルシウムアル
ミネートの製造方法である。Further, according to the present invention, Ca and Al are in a molar ratio of 1
1.8: 7.2 to 12.2: 6.8, and F
A raw material containing at least one of e, Si, Ti, and K is used for 1100 in an atmosphere with an oxygen partial pressure of 4 × 10 4 Pa or more.
℃ by heating below a temperature higher than the melt temperature, a method for producing a calcium aluminate, characterized in that to form calcium aluminate that oxygen radicals containing 10 20 cm -3 or more C 12 A 7.
【００１７】また、本発明の好ましい実施態様として、
前記原料が、ＦｅをＦｅ2Ｏ3換算で０．１〜２質量％、
ＳｉをＳｉＯ2換算で０．１〜４質量％、ＴｉをＴｉＯ2
換算で０．１〜１０質量％、ＫをＫ2Ｏ換算で０．１〜
１質量％を含有することを特徴とする前記のカルシウム
アルミネートの製造方法である。As a preferred embodiment of the present invention,
The raw material contains 0.1 to 2 % by mass of Fe in terms of Fe 2 O 3 ,
Si is 0.1 to 4 mass% in terms of SiO 2 , and Ti is TiO 2.
0.1 to 10 mass% in terms of K, 0.1 to K in terms of K 2 O
The method for producing calcium aluminate is characterized by containing 1% by mass.
【００１８】加えて、本発明は、前記のカルシウムアル
ミネートの製造方法によって得たカルシウムアルミネー
トを粉砕してなる粉末であって、２ｍ2／ｇ以上の比表
面積値を有することを特徴とするカルシウムアルミネー
ト粉末であり、更に、カルシウム（Ｃａ）とアルミニウ
ム（Ａｌ）をモル比で１１．８：７．２〜１２．２：
６．８含有し、２ｍ2／ｇ以上の比表面積値を有するカ
ルシウムアルミネート粉末を、成形し、酸素分圧４×１
０4Ｐａ以上の雰囲気下１１００℃以上溶融温度以下に
加熱してなることを特徴とするカルシウムアルミネート
焼結体である。In addition, the present invention is a powder obtained by pulverizing the calcium aluminate obtained by the above-described method for producing calcium aluminate, which has a specific surface area value of 2 m 2 / g or more. Calcium aluminate powder, further comprising calcium (Ca) and aluminum (Al) in a molar ratio of 11.8: 7.2 to 12.2:
Calcium aluminate powder containing 6.8 and having a specific surface area value of 2 m 2 / g or more is molded to obtain an oxygen partial pressure of 4 × 1.
A calcium aluminate sintered body characterized by being heated to a melting temperature of 1100 ° C. or higher in an atmosphere of 0 4 Pa or higher.
【００１９】[0019]
【発明の実施の形態】本発明の第１は、カルシウム（Ｃ
ａ）とアルミニウム（Ａｌ）をモル比で１１．８：７．
２〜１２．２：６．８含有する非晶質のカルシウムアル
ミネートを原料に用い、前記原料を酸素分圧４×１０4
Ｐａ以上の雰囲気下１１００℃以上溶融温度以下に加熱
することで、当該カルシウムアルミネート中にＣ12Ａ7
を形成し、しかも前記Ｃ12Ａ7が酸素ラジカルを１０20
ｃｍ-3以上含有させることを特徴とするカルシウムアル
ミネートの製造方法である。BEST MODE FOR CARRYING OUT THE INVENTION The first aspect of the present invention is calcium (C
a) and aluminum (Al) in a molar ratio of 11.8: 7.
Amorphous calcium aluminate containing 2 to 12.2: 6.8 is used as a raw material, and the raw material is provided with an oxygen partial pressure of 4 × 10 4.
By heating to 1100 ° C. or higher and a melting temperature or lower in an atmosphere of Pa or higher, C 12 A 7 is added to the calcium aluminate.
And C 12 A 7 forms oxygen radicals 10 20
A method for producing calcium aluminate, characterized in that the calcium aluminate is contained in an amount of at least cm -3 .
【００２０】本発明におけるカルシウムアルミネート
は、主たる成分がＣａ、Ａｌ、酸素（Ｏ）で構成され、
３者の成分合計量が８３質量％以上のものを示す。The calcium aluminate in the present invention is mainly composed of Ca, Al and oxygen (O),
The total amount of the three components is 83% by mass or more.
【００２１】本発明の原料のカルシウムアルミネート
は、ＣａとＡｌをモル比で１１．８：７．２〜１２．
２：６．８含有し、非晶質であり、好ましくは、更にＦ
ｅ、Ｓｉ、Ｔｉ、Ｋのいずれか１種以上を含有する。こ
こで、ＣａとＡｌのモル比が前記範囲外の場合、得られ
るカルシウムアルミネートにおいてＣ12Ａ7が主たる鉱
物相とならない。また、本発明では、Ｆｅ、Ｓｉ、Ｔ
ｉ、Ｋのいずれか１種以上を含有することが好ましく、
これは本発明者が実験的に見いだしたことである。原料
中にＦｅ、Ｓｉ、Ｔｉ、Ｋのいずれか１種以上が存在す
ることにより、存在しない場合、即ち従来技術による場
合に比べて、より低温域で高酸素ラジカル濃度のＣ12Ａ
7が形成することができる。The calcium aluminate as the raw material of the present invention has a molar ratio of Ca and Al of 11.8: 7.2 to 12.
2: 6.8 content, amorphous, preferably F
At least one of e, Si, Ti, and K is contained. Here, when the molar ratio of Ca and Al is out of the above range, C 12 A 7 does not become a main mineral phase in the obtained calcium aluminate. Further, in the present invention, Fe, Si, T
It is preferable to contain any one or more of i and K,
This is what the inventor found experimentally. Due to the presence of one or more of Fe, Si, Ti, and K in the raw material, C 12 A having a high oxygen radical concentration in a lower temperature range than in the absence thereof, that is, the case of the conventional technique.
7 can be formed.
【００２２】前記原料のカルシウムアルミネートは、ア
ルミナセメント成分として知られているもので、石灰
石、消石灰、生石灰、アルミナ、水酸化アルミナ、ボー
キサイト、アルミ残灰等を原料にキルン中での焼成、電
気炉中での溶融等の手段で製造されることで得られる。The above-mentioned raw material calcium aluminate is known as an alumina cement component, and limestone, slaked lime, quicklime, alumina, alumina hydroxide, bauxite, aluminum residual ash, etc. are used as raw materials for firing in a kiln and electrolysis. It is obtained by being manufactured by means such as melting in a furnace.
【００２３】本発明に於いて、カルシウムアルミネート
中に高酸素ラジカル濃度のＣ12Ａ7を生成せしめる条件
として、酸素分圧４×１０4Ｐａ以上の雰囲気下１１０
０℃以上の非溶融温度範囲を選択する。In the present invention, as a condition for producing C 12 A 7 having a high oxygen radical concentration in calcium aluminate, an atmosphere having an oxygen partial pressure of 4 × 10 4 Pa or more is used.
Select a non-melting temperature range above 0 ° C.
【００２４】この条件は、主として原料カルシウムアル
ミネートが非晶質であることに関係している。更に、Ｆ
ｅ、Ｓｉ、Ｔｉ、Ｋのいずれか１種以上が存在すること
にも関係している。また酸素分圧が４×１０4Ｐａ未満
では得られるカルシウムアルミネート中にＣ12Ａ7が形
成されても、当該Ｃ12Ａ7中に酸素ラジカルが１０20ｃ
ｍ-3以上の高濃度にまで含まれていない。This condition is mainly related to that the raw material calcium aluminate is amorphous. Furthermore, F
It is also related to the presence of one or more of e, Si, Ti, and K. Further, when the oxygen partial pressure is less than 4 × 10 4 Pa, even if C 12 A 7 is formed in the obtained calcium aluminate, oxygen radicals are contained in the C 12 A 7 in an amount of 10 20 c.
It is not contained in high concentrations above m -3 .
【００２５】加熱する温度については、温度が高すぎて
溶融状態となると、その冷却状況に応じて得られるカル
シウムアルミネートが非晶質であったり、高酸素ラジカ
ル濃度のＣ12Ａ7を含ませることができない。また、１
１００℃未満では、Ｃ12Ａ7の結晶化の速度が遅いこ
と、更にＣ12Ａ7が形成されていても、その中に酸素ラ
ジカルを包接し難いことから、本発明では前記温度範囲
が選択される。好ましい温度範囲は、１１５０〜１３５
０℃であり、更に、前記範囲において１１５０℃以上１
３００℃未満の範囲を選択するとき従来技術の温度範囲
より低温度で実施できることから、本発明の効果を際立
って高く得ることができ、一層好ましい。Regarding the heating temperature, when the temperature is too high and becomes a molten state, the calcium aluminate obtained is amorphous or contains C 12 A 7 having a high oxygen radical concentration depending on the cooling condition. I can't. Also, 1
If the temperature is lower than 100 ° C., the crystallization rate of C 12 A 7 is slow, and even if C 12 A 7 is formed, it is difficult to include oxygen radicals in the C 12 A 7 , so that the above temperature range is selected in the present invention. To be done. The preferred temperature range is 1150-135
0 ° C., and more than 1150 ° C. in the above range
When the range of less than 300 ° C. is selected, it can be carried out at a temperature lower than the temperature range of the prior art, so that the effect of the present invention can be remarkably enhanced, which is more preferable.
【００２６】原料カルシウムアルミネート中のＦｅ、Ｓ
ｉ、Ｔｉ、Ｋの量については、本発明者の実験的検討結
果に基づけば、ＦｅについてＦｅ2Ｏ3換算で０．１〜２
質量％、ＳｉについてＳｉＯ2換算で０．１〜４質量
％、ＴｉについてＴｉＯ2換算で０．１〜１０質量％、
ＫについてＫ2Ｏ換算で０．１〜１質量％である。いず
れも下限値の０．１質量％以上の存在で、カルシウムア
ルミネート中に高酸素ラジカル濃度のＣ12Ａ7を生成せ
しめる温度条件を低下させることができる。上限値につ
いては、格別の技術的価値を見いだしていないが、それ
ぞれの上限値を超えるような非晶質のカルシウムアルミ
ネートは産業上入手し難い。Fe and S in the raw material calcium aluminate
Regarding the amounts of i, Ti, and K, 0.1 to 2 in terms of Fe 2 O 3 in terms of Fe, based on the results of the experimental study by the present inventors.
% By mass, 0.1 to 4% by mass of Si in terms of SiO 2 , 0.1 to 10% by mass of Ti in terms of TiO 2 ,
About K, it is 0.1 to 1 mass% in terms of K 2 O. In all cases, the presence of 0.1% by mass or more, which is the lower limit value, can reduce the temperature condition for producing C 12 A 7 having a high oxygen radical concentration in calcium aluminate. Regarding the upper limit value, we have not found any particular technical value, but it is difficult to industrially obtain amorphous calcium aluminate that exceeds each upper limit value.
【００２７】本発明の第２は、ＣａとＡｌをモル比で１
１．８：７．２〜１２．２：６．８含有し、しかもＦ
ｅ、Ｓｉ、Ｔｉ、Ｋのいずれか１種以上が含有された原
料を、酸素分圧４×１０4Ｐａ以上の雰囲気下１１００
℃以上１３００℃未満の温度で加熱することで、酸素ラ
ジカル濃度が１０20ｃｍ-3以上のＣ12Ａ7を含有するカ
ルシウムアルミネートを形成させることを特徴とするカ
ルシウムアルミネートの製造方法である。The second aspect of the present invention is that the molar ratio of Ca and Al is 1
1.8: 7.2 to 12.2: 6.8, and F
A raw material containing at least one of e, Si, Ti, and K is used for 1100 in an atmosphere with an oxygen partial pressure of 4 × 10 4 Pa or more.
A method for producing a calcium aluminate, which comprises forming a calcium aluminate containing C 12 A 7 having an oxygen radical concentration of 10 20 cm -3 or more by heating at a temperature of ℃ or more and less than 1300 ° C. .
【００２８】本発明は、本発明者が前記第１の発明を基
に、その改良方法として見いだしたもので、本法によれ
ば非晶質のカルシウムアルミネートに限定されることな
く、従来よりも低温度条件下で、酸素ラジカル濃度が１
０20ｃｍ-3以上のＣ12Ａ7を含有するカルシウムアルミ
ネートを形成させることができる。The present invention was found by the present inventor as an improved method based on the first invention. According to the present method, the present invention is not limited to amorphous calcium aluminate, Even under low temperature conditions, the oxygen radical concentration is 1
0 20 cm -3 to C 12 A 7 or more can be formed calcium aluminate containing.
【００２９】即ち、本発明で用いられる原料としては、
高純度の試薬に限られる必要がなく、非晶質のカルシウ
ムアルミネートの原料となる石灰石、消石灰、生石灰、
アルミナ、水酸化アルミナ、ボーキサイト、アルミ残灰
等を用いることができる。本発明では、特定条件下で加
熱することで固相反応により、酸素ラジカル濃度が１０
20ｃｍ-3以上のＣ12Ａ7を含有するカルシウムアルミネ
ートを形成させるので、当該固相反応を速やかに達成す
る目的で原料を微粉末とし充分混合されていることが望
ましく、２ｍ2／ｇ以上の比表面積を有する原料粉末と
することが好ましい。That is, as the raw material used in the present invention,
There is no need to be limited to high-purity reagents, limestone, slaked lime, quick lime, which is the raw material for amorphous calcium aluminate,
Alumina, alumina hydroxide, bauxite, aluminum residual ash, etc. can be used. In the present invention, by heating under a specific condition, the oxygen radical concentration becomes 10 due to the solid phase reaction.
Since a calcium aluminate containing 20 cm -3 or more of C 12 A 7 is formed, it is desirable that the raw materials be finely powdered and sufficiently mixed for the purpose of rapidly achieving the solid-phase reaction, 2 m 2 / g It is preferable to use a raw material powder having the above specific surface area.
【００３０】本発明においては、前述の原料を用い、第
１の発明における非晶質のカルシウムアルミネートと同
様な組成、即ち、ＣａとＡｌをモル比で１１．８：７．
２〜１２．２：６．８とし、更にＦｅ、Ｓｉ、Ｔｉ、Ｋ
のいずれか１種以上を含ませた組成の原料粉末を調整
し、これを用いて特定条件で処理することにより、酸素
ラジカル濃度が１０20ｃｍ-3以上のＣ12Ａ7を含有する
カルシウムアルミネートを形成させる。In the present invention, using the above-mentioned raw materials, the same composition as the amorphous calcium aluminate in the first invention, that is, Ca and Al in a molar ratio of 11.8: 7.
2-12.2: 6.8, Fe, Si, Ti, K
A raw material powder having a composition containing at least one of the above is prepared and treated under the specific conditions using the raw material powder to obtain a calcium aluminum containing C 12 A 7 having an oxygen radical concentration of 10 20 cm -3 or more. Form a nate.
【００３１】本発明で用いるＦｅ、Ｓｉ、Ｔｉ、Ｋの源
については、酸素分圧４×１０4Ｐａ以上の雰囲気下で
それぞれの酸化物を形成できるもので有ればよい。ま
た、原料粉末への添加量に関しては、第１の発明におい
て記載したのと同じ理由から、ＦｅについてＦｅ2Ｏ3換
算で０．１〜２質量％、ＳｉについてＳｉＯ2換算で
０．１〜４質量％、ＴｉについてＴｉＯ2換算で０．１
〜１０質量％、ＫについてＫ2Ｏ換算で０．１〜１質量
％である。また、本発明で特定する酸素分圧の下限値、
温度領域の下限値、上限値の選択理由は、第１の発明と
同じ理由による。The sources of Fe, Si, Ti and K used in the present invention may be those capable of forming the respective oxides in an atmosphere having an oxygen partial pressure of 4 × 10 4 Pa or more. Regarding the amount added to the raw material powder, for the same reason as described in the first invention, 0.1 to 2 % by mass in terms of Fe 2 O 3 in terms of Fe and 0.1 to 2 in terms of SiO 2 in terms of SiO 2. 4% by mass, 0.1 for Ti in terms of TiO 2
10 to 10% by mass, and K is 0.1 to 1% by mass in terms of K 2 O. Further, the lower limit of the oxygen partial pressure specified in the present invention,
The reason why the lower limit value and the upper limit value of the temperature region are selected is the same as in the first invention.
【００３２】本発明は、前記のカルシウムアルミネート
を粉砕して得られるカルシウムアルミネート粉末であっ
て、２ｍ2／ｇ以上の比表面積値を有することが特徴で
ある。前記製造方法で得られた化合物は、通常、粗い粒
が凝集した塊状で得られる。前記塊状の化合物を、従来
公知の方法で粉砕し、カルシウムアルミネート粉末を得
ることができるが、本方法ではそのうち２ｍ2／ｇ以上
の比表面積値を有するものを選択する。前記特性を有す
る粉末を用いるときに、相対密度が９０％以上にまで緻
密となり、その結果気体通過性が著しく小さく、実質的
に気体通過性のない焼結体を得ることができるし、更
に、前記焼結体を得る際の焼結に伴う寸法変化を小さく
出来るので、生産面で好都合である。尚、前記粉砕に於
いては、カルシウムアルミネートが水硬性を有すること
から、また、アルミネートカルシウムが活性な酸素ラジ
カルを含有することから、水分や還元性の高い物質の存
在しない状態下で粉砕することが好ましい。The present invention is a calcium aluminate powder obtained by pulverizing the above calcium aluminate, and is characterized by having a specific surface area value of 2 m 2 / g or more. The compound obtained by the above-mentioned production method is usually obtained in the form of lumps in which coarse particles are aggregated. The agglomerated compound can be pulverized by a conventionally known method to obtain a calcium aluminate powder. In this method, one having a specific surface area value of 2 m 2 / g or more is selected. When a powder having the above characteristics is used, the relative density becomes dense to 90% or more, and as a result, a gas-permeable material is extremely small, and a sintered body having substantially no gas-permeable material can be obtained. This is convenient in terms of production because the dimensional change due to sintering when obtaining the sintered body can be reduced. In the above pulverization, since calcium aluminate has hydraulic properties, and because aluminate calcium contains active oxygen radicals, pulverization is performed in the absence of water or highly reducing substances. Preferably.
【００３３】また、本発明は、カルシウム（Ｃａ）とア
ルミニウム（Ａｌ）をモル比で１１．８：７．２〜１
２．２：６．８含有し、２ｍ2／ｇ以上の比表面積値を
有するカルシウムアルミネート粉末を、成形し、酸素分
圧４×１０4Ｐａ以上の雰囲気下１１００℃以上溶融温
度以下に加熱してなることを特徴とするカルシウムアル
ミネート焼結体である。前記条件で作成される焼結体
は、相対密度が９０％以上にまで緻密となり、その結果
気体通過性が著しく小さく、実質的に気体通過性のない
性質を有するので、例えば、燃料電池用隔壁に用いる場
合等、ガス通過性が低くしかも酸素ラジカルを輸送する
ことが必要とされる用途向けの焼結体として好適であ
る。In the present invention, the molar ratio of calcium (Ca) and aluminum (Al) is 11.8: 7.2-1.
2.2: Contains 6.8 and forms calcium aluminate powder having a specific surface area value of 2 m 2 / g or more and heats it to a melting temperature of 1100 ° C. or more in an atmosphere having an oxygen partial pressure of 4 × 10 4 Pa or more It is a calcium aluminate sintered body characterized by being formed. The sintered body produced under the above conditions has a relative density of 90% or more, and as a result has a significantly small gas passage property and has substantially no gas passage property. For example, it is suitable as a sintered body for applications where the gas permeability is low and it is necessary to transport oxygen radicals.
【００３４】[0034]
【実施例】〔実施例１〕カルシウム（Ｃａ）とアルミニ
ウム（Ａｌ）をモル比で１２：７に含有し、Ｆｅ、Ｓ
ｉ、Ｔｉ、Ｋを含有した非晶質のカルシウムアルミネー
ト原料を、酸素分圧５×１０4Ｐａの雰囲気で１１００
℃で２時間焼成した。得られた化合物は、ジルコニアを
粉砕媒体として乾式でボールミルにより粉砕すること
で、比表面積３．３ｍ2／ｇの粉末を得た。前記粉末に
ついて、１２ＣａＯ・７Ａｌ2Ｏ3であることをＸ線回折
により確認した。また、前記粉末にはＦｅ2Ｏ3が０．５
質量％、ＳｉＯ2が１．３質量％、ＴｉＯ2が２．０質量
％、Ｋ2Ｏが０．２質量％含有していることをＸＲＦ測
定により確認した。また、前記粉末の室温および７７Ｋ
でのＥＳＲスペクトルを測定した。それぞれの吸収バン
ドの強度からＯ2 -イオンラジカルおよびＯ-イオンラジ
カルの濃度はそれぞれ５×１０20ｃｍ- 3と定量された。EXAMPLES Example 1 Calcium (Ca) and aluminum (Al) were contained at a molar ratio of 12: 7, and Fe, S
Amorphous calcium aluminate raw material containing i, Ti, and K was used for 1100 in an atmosphere with an oxygen partial pressure of 5 × 10 4 Pa.
Calcination was carried out for 2 hours. The obtained compound was pulverized by a ball mill in a dry system using zirconia as a pulverization medium to obtain a powder having a specific surface area of 3.3 m 2 / g. The powder was confirmed to be 12CaO · 7Al 2 O 3 by X-ray diffraction. Further, Fe 2 O 3 is 0.5 in the powder.
By XRF measurement, it was confirmed that the content of S, SiO 2 was 1.3%, TiO 2 was 2.0% and K 2 O was 0.2%. Also, the room temperature of the powder and 77K
ESR spectrum was measured. O 2 from the intensity of the respective absorption band - ion radical and O - ion concentration radicals 5 × 10 20 cm, respectively - have been quantified and 3.
【００３５】〔実施例２〕実施例１で用いた非晶質のカ
ルシウムアルミネート原料を、酸素分圧５×１０4Ｐａ
の雰囲気で１２５０℃で２時間焼成した。得られた化合
物は、ジルコニアを粉砕媒体として乾式で振動ミルによ
り粉砕することで、比表面積２．６ｍ2／ｇの粉末を得
た。前記粉末について１２ＣａＯ・７Ａｌ2Ｏ3であるこ
とをＸ線回折により確認した。またＦｅ2Ｏ3が０．５質
量％、ＳｉＯ2が１．３質量％、ＴｉＯ2が２．０質量
％、Ｋ2Ｏが０．２質量％含有していることをＸＲＦ測
定により確認した。また、室温および７７ＫでのＥＳＲ
スペクトルを測定した。それぞれの吸収バンドの強度か
らＯ2 -イオンラジカルおよびＯ-イオンラジカルの濃度
はそれぞれ７×１０20ｃｍ-3と定量された。Example 2 The amorphous calcium aluminate raw material used in Example 1 was treated with oxygen partial pressure of 5 × 10 4 Pa.
It was fired at 1250 ° C. for 2 hours in the atmosphere. The obtained compound was pulverized by a vibration mill in a dry system using zirconia as a pulverization medium to obtain a powder having a specific surface area of 2.6 m 2 / g. The powder was confirmed to be 12CaO.7Al 2 O 3 by X-ray diffraction. It was also confirmed by XRF measurement that Fe 2 O 3 was contained in an amount of 0.5% by mass, SiO 2 was contained in an amount of 1.3% by mass, TiO 2 was contained in an amount of 2.0% by mass, and K 2 O was contained in an amount of 0.2% by mass. . Also, ESR at room temperature and 77K
The spectrum was measured. From the intensity of each absorption band, the concentrations of O 2 − ion radicals and O − ion radicals were quantified as 7 × 10 20 cm −3 , respectively.
【００３６】〔比較例１〕実施例１において、酸素分圧
４×１０4Ｐａの雰囲気で１０００℃で２時間焼成する
ことで、比較の例とした。得られた粉末についてＦｅ2
Ｏ3が０．５質量％、ＳｉＯ2が１．３質量％、ＴｉＯ2
が２．０質量％、Ｋ2Ｏが０．２質量％含有しているこ
とをＸＲＦ測定により確認したが、Ｘ線回折測定によっ
ては１２ＣａＯ・７Ａｌ2Ｏ3であることが確認できなか
った。また、得られた粉末についてＥＳＲおよびラマン
散乱スぺクトルで調べたところ、Ｏ-イオンラジカルは
検出されず、Ｏ2 -が１×１０19ｃｍ-3であった。Comparative Example 1 In Example 1, a comparative example was obtained by firing at 1000 ° C. for 2 hours in an atmosphere with an oxygen partial pressure of 4 × 10 4 Pa. About the obtained powder Fe 2
0.5% by mass of O 3, 1.3% by mass of SiO 2 , TiO 2
Was confirmed to be 12CaO.7Al 2 O 3 by XRF measurement, although it was confirmed by XRF measurement that the content of 2.0Ca was 2.0 mass% and that of K 2 O was 0.2 mass%. Further, when the obtained powder was examined by ESR and Raman scattering spectrum, no O − ion radical was detected and O 2 − was 1 × 10 19 cm −3 .
【００３７】〔比較例２〕実施例１において、酸素分圧
４×１０4Ｐａの雰囲気で１３５０℃２時間焼成の条件
とすることで比較例とした。１３００℃以上で原料の一
部が溶融していること確認されたが１３５０℃で２時間
焼成した。得られた粉末について１２ＣａＯ・７Ａｌ2
Ｏ3であることをＸ線回折により確認した。また、Ｆｅ2
Ｏ3が０．５質量％、ＳｉＯ2が１．３質量％、ＴｉＯ2
が２．０質量％、Ｋ2Ｏが０．２質量％含有しているこ
とをＸＲＦ測定により確認した。また、得られた粉末に
ついてＥＳＲおよびラマン散乱スぺクトルで調べたとこ
ろ、Ｏ-イオンラジカルは検出されず、Ｏ2 -が１×１０
19ｃｍ-3であった。[Comparative Example 2] A comparative example was obtained by setting the firing conditions in Example 1 at 1350 ° C. for 2 hours in an atmosphere with an oxygen partial pressure of 4 × 10 4 Pa. Although it was confirmed that a part of the raw material was melted at 1300 ° C or higher, it was fired at 1350 ° C for 2 hours. About the obtained powder 12CaO · 7Al 2
It was confirmed to be O 3 by X-ray diffraction. In addition, Fe 2
0.5% by mass of O 3, 1.3% by mass of SiO 2 , TiO 2
Of 2.0% by mass and K 2 O of 0.2% by mass were confirmed by XRF measurement. Further, when the obtained powder was examined by ESR and Raman scattering spectrum, no O − ion radical was detected and O 2 − was 1 × 10 5.
It was 19 cm -3 .
【００３８】〔実施例３〕炭酸カルシウムとα−アルミ
ナをモル比で１２：７の当量混合し、Ｆｅ2Ｏ3が１．０
質量％、ＳｉＯ2が１．９質量％、ＴｉＯ2が３．５質量
％、Ｋ 2Ｏが０．５質量％含有している原料を、酸素分
圧５×１０4Ｐａの雰囲気で１２５０℃で２時間焼成し
た。得られた化合物を、アルミナを粉砕媒体として乾式
でボールミルにより粉砕することで、比表面積２．６ｍ
2／ｇの粉末を得た。前記粉末について１２ＣａＯ・７
Ａｌ2Ｏ3であることをＸ線回折により確認した。また、
前記粉末の室温および７７ＫでのＥＳＲスペクトルを測
定した。それぞれの吸収バンドの強度からＯ2 -イオンラ
ジカルおよびＯ-イオンラジカルの濃度はそれぞれ５×
１０20ｃｍ-3と定量された。[Example 3] Calcium carbonate and α-aluminum
Fe at a molar ratio of 12: 7 and mixed with Fe2O3Is 1.0
Mass%, SiO2Is 1.9% by mass, TiO2Is 3.5 mass
%, K 2A raw material containing 0.5% by mass of O is used as an oxygen component.
Pressure 5 × 10FourBaking at 1250 ° C for 2 hours in Pa atmosphere
It was The obtained compound was dried using alumina as a grinding medium.
The specific surface area is 2.6m
2/ G of powder was obtained. 12CaO · 7 for the powder
Al2O3It was confirmed by X-ray diffraction. Also,
Measure the ESR spectrum of the powder at room temperature and 77K.
Decided O from the intensity of each absorption band2 -AEON LA
Zical and O-Ion radical concentration is 5x each
1020cm-3Was quantified.
【００３９】〔比較例３〕炭酸カルシウムとα−アルミ
ナをモル比で１２：７の当量混合し、Ｆｅ2Ｏ3が３．０
質量％、ＳｉＯ2が５．０質量％、ＴｉＯ2が１０．５質
量％、Ｋ2Ｏが２．０質量％含有している原料を、酸素
分圧５×１０4Ｐａの雰囲気で１２５０℃で２時間焼成
した。得られた化合物を、アルミナを粉砕媒体として乾
式でボールミルにより粉砕することで、比表面積１．５
ｍ2／ｇの粉末を得た。得られた粉末をＸ線回折により
測定したが、１２ＣａＯ・７Ａｌ2Ｏ3であることが確認
できなかった。また、得られた粉末についてＥＳＲおよ
びラマン散乱スぺクトルで調べたところ、Ｏ-イオンラ
ジカルは検出されず、Ｏ2 -が１×１０19ｃｍ- 3であっ
た。Comparative Example 3 Calcium carbonate and α-alumina were mixed in an equivalent ratio of 12: 7, and Fe 2 O 3 was 3.0.
Mass%, SiO 2 5.0 mass%, TiO 2 10.5 mass% and K 2 O 2.0 mass% are contained in an atmosphere with an oxygen partial pressure of 5 × 10 4 Pa at 1250 ° C. It was baked for 2 hours. The obtained compound was pulverized by a ball mill in a dry method using alumina as a pulverization medium to obtain a specific surface area of 1.5.
m 2 / g of powder was obtained. The obtained powder was measured by X-ray diffraction, but it could not be confirmed to be 12CaO · 7Al 2 O 3 . Further, when the obtained powder was examined by ESR and Raman scattering scan Bae spectrum, O - ion radical was not detected, O 2 - is 1 × 10 19 cm - was 3.
【００４０】〔実施例４〕実施例１で得た粉末を成形圧
力５ＭＰａで金型成形し、相対密度５５％の成形体と
し、これを酸素分圧５×１０4Ｐａの雰囲気で１２５０
℃で２時間焼成して、大きさ３０ｍｍ×３０ｍｍ×５ｍ
ｍの焼結体を得た。前記焼結体の相対密度は９７％であ
り、気体通過性を有していなかった。Example 4 The powder obtained in Example 1 was die-molded at a molding pressure of 5 MPa to obtain a compact having a relative density of 55%, which was 1250 in an atmosphere with an oxygen partial pressure of 5 × 10 4 Pa.
Baking at ℃ for 2 hours, size 30mm × 30mm × 5m
A sintered body of m was obtained. The relative density of the sintered body was 97%, and it did not have gas permeability.
【００４１】〔比較例４〕実施例３で用いた原料を成形
圧力５ＭＰａで金型成形し、相対密度５２％の成形体と
し、これを酸素分圧５×１０4Ｐａの雰囲気で１２５０
℃で２時間焼成して、大きさ３０ｍｍ×３０ｍｍ×５ｍ
ｍの焼結体を得ようと試みたところ、相対密度が８０％
で、気体通過性を有する焼結体しか得られなかった。[Comparative Example 4] The raw material used in Example 3 was die-molded at a molding pressure of 5 MPa to obtain a compact having a relative density of 52%, which was 1250 in an atmosphere having an oxygen partial pressure of 5 x 10 4 Pa.
Baking at ℃ for 2 hours, size 30mm × 30mm × 5m
When trying to obtain a sintered body of m, the relative density was 80%
Therefore, only a sintered body having gas permeability was obtained.
【００４２】[0042]
【発明の効果】本発明によれば、実質的にＣ12Ａ7組成
で非晶質のカルシウムアルミネートを用いて、或いは、
実質的にＣ12Ａ7組成に配合され、しかもＦｅ、Ｓｉ、
Ｔｉ、Ｋのいずれか１種以上が含有された原料を用い
て、１０20ｃｍ-3以上の高濃度のＳＯＲを包接するＣ12
Ａ7化合物を低温度条件下で作成することができる特徴
があるので、セメント原料を用いて容易に、酸化触媒、
抗菌剤等の用途に好適な微粉末状のＣ12Ａ7化合物を安
価に得ることができ、産業上非常に有用である。According to the present invention, amorphous calcium aluminate having a substantially C 12 A 7 composition is used, or
Formulated in substantially C 12 A 7 composition, moreover Fe, Si,
C 12 which includes a high-concentration SOR of 10 20 cm −3 or more using a raw material containing at least one of Ti and K
Since the A 7 compound can be prepared under low temperature conditions, it is possible to easily use an oxidation catalyst,
A fine powder C 12 A 7 compound suitable for use as an antibacterial agent or the like can be obtained at a low cost and is very useful industrially.
【００４３】更に、本発明で得られるカルシウムアルミ
ネート粉末は焼結性に富み、緻密で気体透過性が実質的
にない焼結体を容易にえることができ、産業上非常に有
用である。Further, the calcium aluminate powder obtained by the present invention has a high sinterability, can easily form a dense sintered body having substantially no gas permeability, and is industrially very useful.
Claims (5)
ｌ）をモル比で１１．８：７．２〜１２．２：６．８含
有し、しかも非晶質のカルシウムアルミネートを原料に
用い、前記原料を酸素分圧４×１０4Ｐａ以上の雰囲気
下１１００℃以上溶融温度以下に加熱することで、当該
カルシウムアルミネート中に１２ＣａＯ・７Ａｌ2Ｏ
3（以下、Ｃ12Ａ7という）を形成し、しかも前記Ｃ12Ａ
7が酸素ラジカルを１０20ｃｍ-3以上含有させることを
特徴とするカルシウムアルミネートの製造方法。1. Calcium (Ca) and aluminum (A
1) in a molar ratio of 11.8: 7.2 to 12.2: 6.8, and using amorphous calcium aluminate as a raw material, the raw material having an oxygen partial pressure of 4 × 10 4 Pa or more. By heating to 1100 ° C. or higher and a melting temperature or lower in an atmosphere, 12CaO · 7Al 2 O is contained in the calcium aluminate.
3 (hereinafter, referred to as C 12 A 7 ) is formed, and the above C 12 A is formed.
7. The method for producing calcium aluminate, wherein 7 contains 10 20 cm −3 or more of oxygen radicals.
１２．２：６．８含有し、しかもＦｅ、Ｓｉ、Ｔｉ、Ｋ
のいずれか１種以上が含有された原料を、酸素分圧４×
１０4Ｐａ以上の雰囲気下１１００℃以上溶融温度以下
の温度に加熱することで、酸素ラジカルを１０20ｃｍ-3
以上のＣ12Ａ7を含有するカルシウムアルミネートを形
成させることを特徴とするカルシウムアルミネートの製
造方法。2. A molar ratio of Ca and Al of 11.8: 7.2.
12.2: 6.8 contained, and Fe, Si, Ti, K
The oxygen partial pressure of the raw material containing one or more of
By heating to a temperature of 1100 ° C. or higher and a melting temperature or lower in an atmosphere of 10 4 Pa or higher, oxygen radicals are heated to 10 20 cm −3.
A method for producing calcium aluminate, which comprises forming the above calcium aluminate containing C 12 A 7 .
〜２質量％、ＳｉをＳｉＯ2換算で０．１〜４質量％、
ＴｉをＴｉＯ2換算で０．１〜１０質量％、ＫをＫ2Ｏ換
算で０．１〜１質量％を含有することを特徴とする請求
項１又は請求項２記載のカルシウムアルミネートの製造
方法。3. The raw material is Fe which is 0.1 in terms of Fe 2 O 3.
˜2% by mass, Si in terms of SiO 2 of 0.1 to 4% by mass,
3. The production of calcium aluminate according to claim 1 or 2, wherein Ti is contained in an amount of 0.1 to 10% by mass in terms of TiO 2 and K is contained in an amount of 0.1 to 1% by mass in terms of K 2 O. Method.
ルシウムアルミネートの製造方法によって得たカルシウ
ムアルミネートを粉砕してなる粉末であって、２ｍ2／
ｇ以上の比表面積値を有することを特徴とするカルシウ
ムアルミネート粉末。4. A powder obtained by pulverizing calcium aluminate obtained by the method for producing calcium aluminate according to claim 1, 2 or 3, which has a particle size of 2 m 2 /
A calcium aluminate powder having a specific surface area value of g or more.
ｌ）をモル比で１１．８：７．２〜１２．２：６．８含
有し、２ｍ2／ｇ以上の比表面積値を有するカルシウム
アルミネート粉末を、成形し、酸素分圧４×１０4Ｐａ
以上の雰囲気下１１００℃以上溶融温度以下に加熱して
なることを特徴とするカルシウムアルミネート焼結体。5. Calcium (Ca) and aluminum (A
1) in a molar ratio of 11.8: 7.2 to 12.2: 6.8, and a calcium aluminate powder having a specific surface area value of 2 m 2 / g or more is molded to obtain an oxygen partial pressure of 4 × 10. 4 Pa
A calcium aluminate sintered body characterized by being heated to a melting temperature of 1100 ° C. or higher in the above atmosphere.
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| JP2002030742A JP4056258B2 (en) | 2002-02-07 | 2002-02-07 | Method for producing oxygen radical-containing calcium aluminate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002030742A JP4056258B2 (en) | 2002-02-07 | 2002-02-07 | Method for producing oxygen radical-containing calcium aluminate |
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| JP2003226571A true JP2003226571A (en) | 2003-08-12 |
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| JP4056258B2 JP4056258B2 (en) | 2008-03-05 |
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