JPS62182154A - Calcia sintered body and manufacture - Google Patents
Calcia sintered body and manufactureInfo
- Publication number
- JPS62182154A JPS62182154A JP61022975A JP2297586A JPS62182154A JP S62182154 A JPS62182154 A JP S62182154A JP 61022975 A JP61022975 A JP 61022975A JP 2297586 A JP2297586 A JP 2297586A JP S62182154 A JPS62182154 A JP S62182154A
- Authority
- JP
- Japan
- Prior art keywords
- calcia
- sintered body
- less
- weight
- crystals
- 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
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 title claims description 103
- 239000000292 calcium oxide Substances 0.000 title claims description 90
- 235000012255 calcium oxide Nutrition 0.000 title claims description 90
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000013078 crystal Substances 0.000 claims description 26
- 238000010304 firing Methods 0.000 claims description 24
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 23
- 239000000920 calcium hydroxide Substances 0.000 claims description 23
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 7
- 150000003755 zirconium compounds Chemical class 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- -1 aluminum compound Chemical class 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 235000011116 calcium hydroxide Nutrition 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 230000029087 digestion Effects 0.000 description 19
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 13
- 238000005245 sintering Methods 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000011819 refractory material Substances 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 235000010216 calcium carbonate Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000019621 digestibility Nutrition 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000009628 steelmaking Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011822 basic refractory Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- RGRFMLCXNGPERX-UHFFFAOYSA-L oxozirconium(2+) carbonate Chemical compound [Zr+2]=O.[O-]C([O-])=O RGRFMLCXNGPERX-UHFFFAOYSA-L 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
ｉ泉よＬ■ユ匁１
本発明は製鋼炉用耐大物の原料に適する高純度、高密度
かつ耐消化性に優れるカルシア焼結体およびその製造法
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a calcia sintered body having high purity, high density and excellent digestion resistance and suitable as a raw material for large-sized products for steel-making furnaces, and a method for producing the same.
従来の技術
近年、製鋼業ではますます鋼の高級化や連続鋳造等、操
業の合理化への志向が強まり、転炉や取鋼の高温化、あ
るいは取鍋製錬法の導入が行なわれている。そのため転
炉や取鍋製錬炉に使用される耐火物に対して従来用いら
れできた。マグネシア・カーボン貿、マグネシア・クロ
ム貿、ハイアルミナ貿、ジルコン貿耐火物よりもより苛
酷な条件に耐えるものが望まれている。Conventional technology In recent years, there has been a growing trend in the steel manufacturing industry toward streamlining operations, such as using higher-grade steel and continuous casting, leading to the introduction of converter furnaces, higher temperatures for steel taps, and ladle smelting methods. . Therefore, it has traditionally been used for refractories used in converters and ladle smelting furnaces. Refractories that can withstand harsher conditions than magnesia-carbon, magnesia-chromium, high-alumina, and zircon refractories are desired.
塩基性耐火物材料として、カルシアは融点が２５８０℃
と高く、耐熱衝撃性、耐スラグ侵食性が高く、また鋼中
介在物のＡ Ｉ ２０３を吸収するなど優れた性質を持
っている。我国では資源的にも恵まれていることから、
製鋼炉用耐大物として大いに期待されている。それにも
関わらず、カルシア質耐火物はまだ本格的に実用化され
ていない。その大きな理由は耐火物の原料となるカルシ
アクリンカ−（カルシア焼結体をカルシアクリンカ−と
呼ぶ）は、水に耐する耐消化性が低く、取扱い、貯蔵あ
るいは煉瓦製造に難点かめること、および高密度焼結体
が得られいないため、耐スラグ性、および強度に問題が
あることなどである。従ってカルシア質耐大物を工業的
に利用するには、カルシアクリンカ−の耐消化性と嵩密
度の改善が大きな課題である。耐消化性と嵩密度とは密
接な関係があり、嵩密度を高めることにより耐消化性も
改善される。それ故、嵩密度を高めることは耐消化性を
高める上で重要な要件の１つである。As a basic refractory material, calcia has a melting point of 2580℃
It has excellent properties such as high thermal shock resistance, high slag erosion resistance, and ability to absorb A I 203 inclusions in steel. Since our country is rich in resources,
It is highly anticipated as a large-sized material for steelmaking furnaces. Despite this, calcia refractories have not yet been put into full-scale practical use. The main reason for this is that calcia clinker (calcia sintered body is called calcia clinker), which is the raw material for refractories, has low water resistance and digestion resistance, which poses difficulties in handling, storage, and brick manufacturing. Since a dense sintered body cannot be obtained, there are problems with slag resistance and strength. Therefore, in order to industrially utilize large calcia-based materials, it is a major issue to improve the digestibility and bulk density of calcia clinker. There is a close relationship between digestibility and bulk density, and increasing bulk density also improves digestibility. Therefore, increasing the bulk density is one of the important requirements for increasing the digestion resistance.
密度を高めることの他に、カルシアクリンカ−の耐消化
性を改善する方法として、種々の方法が提案されている
。たとえば、石灰質原料にＦｅ２Ｏ３２〜１０重担％、
ＭｇＯ１〜５重量％、ＳｉＯ２２小母％以下になる様に
、各成分を添加調合して、この原料を加圧成形した後に
１３５０〜１６５０℃で焼成する方法（特開昭５５−９
５６１４＠公報）周期律表第■族または第１ｖ族元素の
化合物の１種と弗化カルシウムをあわせて添加する方法
（特開昭５６−１４４５７号公報＞ ＣａＯまたはＣａ
ＯとＭｇＯを主成分とし、Ｆ ｅ ２０ ］ ０．４
〜１．２ ｍ５ｉ％、ＴｉＯ２０，１〜０．５重量％、
Ｓ ！ ０２１．５手ω％以下、Ａｌ２０３１．０単■
％以下を含み、かつＦｅ２Ｏ］、ＴｉＯ２，５ｉＯｚ、
Ａ Ｉ ２０３の合量が０．５〜３重足％とする方法（
特開昭５９−３５０６０号公報）などがある。In addition to increasing the density, various methods have been proposed to improve the digestibility of calcia clinker. For example, 2 to 10% Fe2O3 in calcareous raw material,
A method in which each component is added and mixed so that MgO is 1 to 5% by weight and SiO2 is 2% or less, and this raw material is pressure-molded and then fired at 1350 to 1650°C (Japanese Patent Laid-Open No. 55-9
5614@publication) A method of adding calcium fluoride together with one kind of compound of Group Ⅰ or Group 1V elements of the periodic table (JP-A-56-14457 > CaO or Ca
The main components are O and MgO, and F e 20 ] 0.4
~1.2 m5i%, TiO20.1-0.5% by weight,
S! 021.5 hand ω% or less, Al2031.0 single■
% or less, and Fe2O], TiO2,5iOz,
A method in which the total amount of A I 203 is 0.5 to 3% (
JP-A No. 59-35060).
これらはＣａＯに一定の不純物を添加することによって
、ＣａＯの焼結温度を下げ、緻密化を促進し、ＣａＯ結
晶の表面を低融点化合物で覆うことにより、耐消化性を
得ようとする方法である。また、高純度でかつ微細な一
定粒度の消石灰を出発原料とし、１８００℃以上の高温
度で焼成することによって、高い耐消化性を有するカル
シア焼結体を得る方法（特開昭６０−５１６５８号公報
）が提案されている。These are methods that attempt to obtain digestion resistance by adding certain impurities to CaO to lower the sintering temperature of CaO, promoting densification, and covering the surface of CaO crystals with a low-melting compound. be. In addition, a method for obtaining a calcia sintered body with high digestion resistance by using slaked lime of high purity and a constant fine particle size as a starting material and firing it at a high temperature of 1800°C or higher (Japanese Patent Laid-Open No. 60-51658) Public bulletin) has been proposed.
発明が解決しようとする問題点
上記方法において、ＣａＯにＣａＯと低融点化合物を形
成する添加物を多岳に添加することは、熱間強度および
高温安定性の低下を招くため、耐消化性の改善には効果
があるものの、カルシア質耐火物の本来の優れた特性を
劣化させる欠点を右づる。また特開昭６ｏ−５１６５８
号公報の高純度微粒消石灰を高温焼成する方法は焼成温
度が１８００℃以上と高く、多量のエネルギーを必要と
するのにも関わらず、得られるカルシア焼結体の嵩密度
は相対密度で９０〜９３％でおり、全気孔率か７〜１０
％でおる。これは通常製鋼炉用耐大物の原料として使用
されているマグネシアクリンカ−の相対密度（９７％）
と比べてかなり低レベルでおり、耐スラグ性や強度の点
で好ましくない。また、この様な密度では高い耐消化性
は期待できない。Problems to be Solved by the Invention In the above method, adding many additives that form low melting point compounds with CaO to CaO leads to a decrease in hot strength and high temperature stability, and therefore reduces digestion resistance. Although the improvement is effective, there are drawbacks that degrade the originally excellent properties of calcia refractories. Also, Unexamined Japanese Patent Publication No. 6o-51658
Although the method of high-temperature firing of high-purity fine slaked lime in the publication requires a high firing temperature of 1,800°C or higher and a large amount of energy, the bulk density of the calcia sintered body obtained is 90 to 90% in relative density. It is 93%, and the total porosity is 7 to 10.
It's %. This is the relative density (97%) of magnesia clinker, which is normally used as a raw material for large materials for steelmaking furnaces.
This is at a considerably lower level than that of the conventional steel, and is not desirable in terms of slag resistance and strength. Furthermore, high digestion resistance cannot be expected at such a density.
カルシアクリンカ−には高純度かつ高い耐消化性が望ま
れてあり、また嵩密度についても耐消化だけでなく、耐
スラグ、強度の点からマグネシアクリンカ−と同等また
はそれ以上の水準のものが要望されている。Calcia clinker is desired to have high purity and high digestion resistance, and it is also desired that the bulk density is equivalent to or higher than magnesia clinker in terms of not only digestion resistance but also slag resistance and strength. has been done.
本発明の目的は、耐消化性に優れ、かつ高密度、高純度
なカルシア焼結体、およびその製造方法を提供すること
にある。An object of the present invention is to provide a calcia sintered body that has excellent digestion resistance, high density, and high purity, and a method for producing the same.
問題点を解決するための手段
本発明者らは、カルシアの焼結に与える添加物の影響、
および得られたカルシア焼結体の構造と耐消化性を中心
に研究を重ねた結果、少量のＡ Ｉ ２０３とＺｒｏ２
を共存さゼて焼結すると、従来１ｑられなかった高密度
かつ大結晶を有するカルシア焼結体か得られることを見
出した。ざらにこの焼結体は従来のものに比へ、非常に
耐消化性に優れることを見出し、その製造法を確立した
。そして、その構成は特許請求の範囲に記載のとおりで
ある。Means for Solving the Problems The present inventors have investigated the effects of additives on the sintering of calcia;
As a result of repeated research focusing on the structure and digestion resistance of the obtained calcia sintered body, we found that a small amount of A I 203 and Zro2
It has been found that by sintering in the coexistence of 1Q, a calcia sintered body having a high density and large crystals, which could not be obtained conventionally, can be obtained. It was discovered that this sintered body has much better resistance to digestion than conventional sintered bodies, and a method for its production was established. The configuration is as described in the claims.
本発明のカルシア焼結体の純度は発明の目的からしてＣ
ａＯで９７．５重１％以上とする。From the purpose of the invention, the purity of the calcia sintered body of the present invention is C
The aO content should be 97.5% by weight or more.
嵩密度は３．２０ ｇ／ｃｃ以上、好ましくは３．２６
９／ＣＣ以上が要求され、かつカルシア結晶の平均径は
６０μｍ以上、好ましくは８０μｍ以上でなくてはなら
ない。嵩密度とカルシア結晶の平均径が上記範囲に同時
に満足されなければ、高い耐消化性、高い耐スラグ侵蝕
性、および強度は得られない。Bulk density is 3.20 g/cc or more, preferably 3.26
9/CC or more is required, and the average diameter of calcia crystals must be 60 μm or more, preferably 80 μm or more. Unless the bulk density and the average diameter of calcia crystals are simultaneously satisfied within the above ranges, high digestion resistance, high slag corrosion resistance, and strength cannot be obtained.
本発明のカルシア焼結体は、灼熱基準でＡ Ｉ ２０３
０．０５重量％以上０．５重量％以下、ＺｒＯ２０，１
重量％以上、１．０重量％以下を含有し、好ましくはＡ
１２０ｔ０．１平担％を越えて、０．２重量％以下、Ｚ
ｒＯ２０，１重量％以上、０．５型組％未満を含有する
。灼熱基準でＡ Ｉ ２０３が０．５重量％を越えても
、嵩密度、カルシア結晶の粒径に及ぼす効果は飽和し、
また耐消化性についても変化しない。The calcia sintered body of the present invention has an A I 203 rating based on scorching heat.
0.05% by weight or more and 0.5% by weight or less, ZrO20.1
Contains at least 1.0% by weight, preferably A
120t more than 0.1% by weight and less than 0.2% by weight, Z
Contains rO20.1% by weight or more and less than 0.5% by weight. Even if A I 203 exceeds 0.5% by weight based on scorching heat, the effect on bulk density and grain size of calcia crystals is saturated,
There is also no change in digestion resistance.
しかしながら、Ａ Ｉ ２０３はＣａＯと反応して、１
４００℃付近でＣａＯＡ ＋ ２０３系の液相を形成す
るため、強度および耐火度の低下を招くので０．５重量
％を上限とする。下限は灼熱基準でＡ Ｉ ２０３０．
０５重平担であり、それよりＡ Ｉ ２０３が少ないと
平均粒径６０μｍ以上のカルシア結晶は得られない。灼
熱基準でＺ ｒ Ｏ２がｉ、ｏ重量％を越えるとＺ ｒ
Ｏ２のカルシア結晶に対する粒径抑制作用により、平
均粒径６０μｍ以上のカルシア結晶は得られない。灼熱
基準でＺ ｒ Ｏ２が０．１重量％より少ないと、高密
度３．２０ （Ｊ／ＣＣ以上の高密度焼結体は得られな
い。また、カルシア焼結体の嵩密度およびカルシア結晶
の平均粒径に与えるＡ Ｉ ２０３、Ｚ ｒ 、０２の
効果は、両者が共存して初めて作用するものであり、上
記組成範囲をＡ Ｉ ２ Ｑ ３ 、Ｚ ｒＱ２のいず
れか一方がはずれても、嵩密度３．２０ ！；ｌ／ＣＣ
以上、カルシア結晶の平均粒径が６０μｍ以上、および
充分な強度を持ったカルシア焼結体は得られない。灼熱
基準で、Ａ Ｉ ２０３が０．１重量％を越えて０．３
重量％以下、かつ、Ｚ ｒ Ｏ２が０．１重量％以上、
０．５重量％未満の時、１ｑられるカルシア焼結体は、
ざらに高密度になり、カルシア結晶の平均粒径も大きく
なる。However, A I 203 reacts with CaO, resulting in 1
Since a CaOA + 203-based liquid phase is formed at around 400° C., this leads to a decrease in strength and fire resistance, so the upper limit is set at 0.5% by weight. The lower limit is A I 2030 based on the scorching heat standard.
If A I 203 is less than that, calcia crystals with an average grain size of 60 μm or more cannot be obtained. If Z r O2 exceeds i, o weight % on scorching heat basis, Z r
Due to the particle size suppressing effect of O2 on calcia crystals, calcia crystals with an average particle size of 60 μm or more cannot be obtained. If Z r O2 is less than 0.1% by weight on a sintering basis, a high density sintered body with a high density of 3.20 (J/CC or higher) cannot be obtained. Also, the bulk density of the calcia sintered body and the calcia crystal The effects of A I 203, Z r , and 02 on the average particle size only work when they coexist, and even if either A I 2 Q 3 or Z rQ2 deviates from the above composition range, Bulk density 3.20!; l/CC
As described above, a calcia sintered body having an average grain size of calcia crystals of 60 μm or more and sufficient strength cannot be obtained. By scorching heat standard, A I 203 exceeds 0.1% by weight and 0.3
% by weight or less, and Z r O2 is 0.1% by weight or more,
When the amount is less than 0.5% by weight, the calcia sintered body is
The density becomes higher and the average grain size of the calcia crystals becomes larger.
従来、カルシアクリンカ−焼成の際に
Ａｌ２Ｏ３は焼結助剤、および消化防止剤として有効で
おると考えられているが、本発明者らにより、Ａｌ２Ｏ
３は１２００℃付近から焼結に有害なＣａＯ粒子の粒成
長を促進するために、結果として相対密度９７％を越え
る様な高密度領域ではむしろ密度を下げる方向に動くこ
とが見出された。ざらに、本発明者らによりＺ ｒ Ｏ
２はＣａＯと低融点化合物を形成せず、かつカルシア粒
子およびカルシア結晶の粒成長を抑制するためにＺ ｒ
Ｏ２を添加焼成したカルシア焼結体は、非常に高密度
になることが見出された。ただし、この時カルシア結晶
の平均粒径は小さくなり、高い耐消化性は１ｑられない
。本発明者らは以上の様に全く異なる効果を発揮するＡ
ｌ２Ｏ３とＺ
ｒＯ２を同時に添加して焼成することにより、従来見ら
れなかった高密度かつ大結晶を有するカルシア焼結体が
１９られることを見出した。Conventionally, Al2O3 is considered to be effective as a sintering aid and anti-digestion agent during calcia clinker firing, but the present inventors have discovered that Al2O
3 promotes the grain growth of CaO particles harmful to sintering from around 1200°C, and as a result, it has been found that in high-density regions where the relative density exceeds 97%, the density tends to decrease. In general, Z r O
2 is Zr in order not to form a low melting point compound with CaO and to suppress grain growth of calcia particles and calcia crystals.
It has been found that a calcia sintered body calcined with the addition of O2 has a very high density. However, at this time, the average particle size of the calcia crystals becomes small, and high digestion resistance cannot be achieved by 1q. As described above, the present inventors have proposed an A method that exhibits completely different effects.
It was discovered that by adding l2O3 and ZrO2 at the same time and firing, a calcia sintered body having a high density and large crystals, which had never been seen before, could be produced19.
カルシア焼結体の高密度化と大結晶化が、同時に達成さ
れる理由として、ＣａＯが緻密化する温度付近でＺ ｒ
Ｏ２が緻密化に有害な粒成長、およびネック形成を抑
制し、緻密化以後の高い温度領域ではＣａ０Ａ＋２０３
系の液相、またはｃａｏ Ａ ｌ ２０３−Ｚ ｒ
Ｏ２系の液相が微量生成し、カルシア結晶の成長を促進
するものと推定される。第１図および第２図に焼成温度
によるカルシア結晶の粒子径、および嵩密度に及ぼす
Ａｌ２Ｏ：ｌ、ＺｒＯ２の影響を示した。The reason why high density and large crystallization of the calcia sintered body are achieved at the same time is that Z r
O2 suppresses grain growth and neck formation that are harmful to densification, and in the high temperature range after densification, Ca0A+203
liquid phase of the system, or cao A l 203-Z r
It is estimated that a small amount of O2-based liquid phase is generated and promotes the growth of calcia crystals. Figures 1 and 2 show the effects of Al2O:l and ZrO2 on the particle size and bulk density of calcia crystals depending on the firing temperature.
第１ 図ハＡ Ｉ ２０３およびＺ ｒ Ｏ２を含むカ
ルシア焼結体におけるカルシア結晶の平均粒子径と焼成
温度おＪ：びＡｌ２Ｏ：ｌおよびＺ ｒ Ｏ２の含有量
との関係を示したグラフである。FIG. 1 is a graph showing the relationship between the average particle diameter of calcia crystals, firing temperature, and content of Al2O:l and ZrO2 in a calcia sintered body containing AI 203 and ZrO2. .
第２図は同じ試料における各焼成温度と嵩密度の関係を
示すグラフである。FIG. 2 is a graph showing the relationship between each firing temperature and bulk density for the same sample.
これらのグラフに画かれた線はそれぞれＡ Ｉ ２０３
およびＺ ｒ ０２を下記のとあり含有している試料に
ついて上記関係を示したものである。なお、下記の（％
）は重量基準で必る。Each line drawn on these graphs is A I 203
The above relationship is shown for the samples containing Z r 02 and Z r 02 as shown below. In addition, the following (%
) is required on a weight basis.
線 Ａｌ ２０３ （％）Ｚｒ０２（％）実線１
０．０２ −実線２ ０．０２
０．２点線３ ０．０６
一点線４ ０．０６ ０．２
この図からカルシア焼結体中にＡ Ｉ ２０３とＺ ｒ
Ｑ ２が同時に、かつ微量存在して初めて、本発明に
よる高密度かつ大結晶を有するカルシア焼結体が得られ
ることが明らかである。Line Al 203 (%) Zr02 (%) Solid line 1
0.02 - solid line 2 0.02
0.2 dotted line 3 0.06
Dotted line 4 0.06 0.2
From this figure, A I 203 and Z r are present in the calcia sintered body.
It is clear that the calcia sintered body having high density and large crystals according to the present invention can be obtained only when Q 2 is simultaneously present in a small amount.
本発明によるカルシア焼結体は、組成が灼熱基準で、重
量％で表わして、
ＱａＱ ９７．５以上
Ａｌ２Ｏ３０，０５以上０．５以下
Ｚｒ０ｚ ０．１以上１．Ｏ以下
および残部が不可避の不純物からなる様に（ａ） ４４
μｍ以下の粒子が９８重量％以上を占め、かつＧＯ２含
有量がＣａ（ＯＨ）２３ｆｆｌ準で５．０重量％以下の
水酸化カルシウム
（ｂ） Ａ Ｉ ２０３または熱分解してＡ Ｉ ２０
３となるアルミニウム化合物
（ｃ）ＺｒＯｚまたは熱分解してＺ ｒ ０２となるジ
ルコニウム化合物を混合することにより、組成調整をし
た原料をそのままで、あるいは加圧して成形体とした後
に、１５００℃以上で焼成することにより製造すること
ができる。The calcia sintered body according to the present invention has a composition expressed in weight percent based on scorching heat: QaQ: 97.5 or more Al2O3 0.05 or more, 0.5 or less Zr0z 0.1 or more1. (a) 44 so that O and below and the remainder consist of unavoidable impurities.
Calcium hydroxide (b) A I 203 or A I 20 by thermal decomposition, with particles of μm or less accounting for 98% by weight or more and a GO2 content of 5.0% by weight or less based on Ca(OH)23ffl
By mixing the aluminum compound (c) ZrOz or the zirconium compound that thermally decomposes to become Z r 02, the composition of the raw material is adjusted as it is or after being pressed into a molded product, it is heated at 1500°C or higher. It can be manufactured by firing.
原料の１つである水酸化カルシウムは４４μｍ以下の粒
子が９８重量％以上を占めなければならない。この様な
水酸化カルシウムは、石灰石または合成炭酸カルシウム
等を仮焼して得た生石灰を水中、好ましくは温水中で消
和して、得られたスラリーを湿式篩分あるいは液体サイ
クロン等を用いて分級することにより得られる。４４μ
ｍ以上の粒子は焼結に有害であり、高密度焼結体を得る
ためには、この様な粒子は除かなくてはならない。ざら
に生石灰は不純物としてＳｉＯ２、Ａｌ２Ｏ３、ＭｑＯ
，Ｆｅ２Ｏ３、ＣａＣＯ３等を多量に含有する場合が多
いが、上記操作に、より、これら不純物を多量に除去す
ることが可能でおる。本発明によるカルシア焼結体はＣ
ａＯを９７．５重量％以上、好ましくは９８．０重量％
以上含有するが、この様な組成を得るためには水酸化カ
ルシウムの純度は灼熱基準でＣａＯとして９９重小母以
上でなければならない。ざらに水酸化カルシウムはＣＯ
２含有量が
Ｃａ （ＯＨ）２基準で５．０重量％以下でなければな
らない。水酸化カルシウムのＣＯ２含有量が５．０重量
％を越えると、嵩密度３．２０ｐ／ＣＣ以上の高密度カ
ルシア焼結体は得られない。これは、水酸化カルシウム
中ではＣＯ２がＣａＣＯ３として含有され、焼成時に９
００℃付近で分解が起こり、ＣＯ２ガスの発生と体積収
縮により空隙が形成されるためと推定される。水酸化カ
ルシウムは容易に空気中のＣＯ２と反応し、またこの様
にして生成したＣａＣＯｘは分級により除去することが
困難なため、注意が必要である。Calcium hydroxide, one of the raw materials, must contain 98% or more by weight of particles of 44 μm or less. Such calcium hydroxide is produced by sintering quicklime obtained by calcining limestone or synthetic calcium carbonate in water, preferably warm water, and then using a wet sieve or a liquid cyclone to slake the resulting slurry. Obtained by classification. 44μ
Particles larger than m are harmful to sintering, and must be removed in order to obtain a high-density sintered body. Quicklime contains SiO2, Al2O3, MqO as impurities.
, Fe2O3, CaCO3, etc., in many cases, but by the above operation, it is possible to remove a large amount of these impurities. The calcia sintered body according to the present invention is C
aO at 97.5% by weight or more, preferably 98.0% by weight
However, in order to obtain such a composition, the purity of calcium hydroxide must be 99 or higher as CaO based on the scorching heat standard. Calcium hydroxide is CO
2 content must be 5.0% by weight or less based on Ca(OH)2. If the CO2 content of calcium hydroxide exceeds 5.0% by weight, a high-density calcia sintered body having a bulk density of 3.20 p/CC or more cannot be obtained. This is because CO2 is contained as CaCO3 in calcium hydroxide, and 9
It is presumed that this is because decomposition occurs at around 00°C, and voids are formed due to the generation of CO2 gas and volumetric contraction. Calcium hydroxide easily reacts with CO2 in the air, and CaCOx generated in this way is difficult to remove by classification, so care must be taken.
本発明において用いられるアルミニウムおよびジルコニ
ウム化合物は、酸化物もしくは熱分解して酸化物となる
化合物でなくてはならない。すなわち、アルミニウム化
合物としては、Ａｌ２Ｏ３、ＡＩ （ＯＨ）３、ＡｌＣ
ｌ３、ＡＩ （ＮＯ３）３、
Ａｌ２（ＳＯ４）３等であり、ジルコニウム化合物とし
ては、ＺｒＯ２、Ｚｒ０ＣＩ ２、酢酸ジルコニル、硝
酸ジルコニル、炭酸ジルコニル等である。使用する化合
物は、市販されている工業用薬品でもよいが、純度が高
いこと、粉末のものは微粒であることが望ましい。通常
、消石灰は前述のように不純物として、Ａｌ２Ｏ３が含
有し、分級精製した消石灰においても本発明において規
定されるＡ Ｉ ２０３含量が達成されることもあり得
る。The aluminum and zirconium compounds used in the present invention must be oxides or compounds that become oxides upon thermal decomposition. That is, aluminum compounds include Al2O3, AI(OH)3, AlC
Zirconium compounds include ZrO2, Zr0CI2, zirconyl acetate, zirconyl nitrate, and zirconyl carbonate. The compound used may be a commercially available industrial chemical, but it is desirable that the purity is high and that the powder is fine. Normally, slaked lime contains Al2O3 as an impurity as described above, and the A I 203 content specified in the present invention may be achieved even in classified and purified slaked lime.
この様な場合はジルコニウム化合物のみを混合する。In such a case, only the zirconium compound is mixed.
本発明において焼成に至るまでの製造工程として原料ス
ラリーを濾過した後に得られたケーキを、
（１）直接焼成する
（２）乾燥した後に、加圧成形をして焼成する（３）仮
焼した後に加圧成形をして焼成するの３つの工程のうち
、いずれか１つをとることができる。いずれの工程にお
いても、水酸化カルシウムとアルミニウム化合物とジル
コニウム化合物の混合は十分均一に混合されることが望
ましく、水酸化カルシウムスラリー中での攪拌による混
合、濾過ケーキ中での混練による混合等が好ましい。（
２）の工程をとる場合は、水酸化カルシウムスラリーを
濾過、乾燥した後に乾式で混合することも可能である。In the present invention, as a manufacturing process up to baking, the cake obtained after filtering the raw material slurry is (1) directly baked, (2) after drying, pressure molded and baked, (3) calcined. Any one of the three steps of subsequent pressure molding and firing can be used. In any process, it is desirable that the calcium hydroxide, aluminum compound, and zirconium compound are mixed sufficiently uniformly, and mixing by stirring in a calcium hydroxide slurry, mixing by kneading in a filter cake, etc. is preferable. . (
When taking step 2), it is also possible to dry mix the calcium hydroxide slurry after filtering and drying it.
また（３）の工程をとる場合には水酸化カルシウムを仮
焼して酸化カルシウムとした後に、混合を行っても何等
差し支えない。ただしこの場合には用いるアルミニウム
およびジルコニウム化合物は酸化物であることが望まし
い。上記いずれの工程においても濾過は通常用いられる
濾過機、たとえば真空濾過機、加圧濾過機等を使用する
ことができる。In addition, when step (3) is used, there is no problem even if calcium hydroxide is calcined to form calcium oxide and then mixed. However, in this case, the aluminum and zirconium compounds used are preferably oxides. In any of the above steps, a commonly used filter, such as a vacuum filter or a pressure filter, can be used for filtration.
（２）の工程をとる場合には、乾燥工程が必要であり、
通常用いられる乾燥機を用いることかできる。ただし、
乾燥に化石燃おｌ燃焼ガスを用いる場合は、ＣＯ２の吸
収は
Ｃａ （ＯＨ）２基準で５．０重量％以下に押さえるこ
とが必要である。ＣＯ２の吸収がない点で空気雰囲気下
の乾燥が望ましい。また、乾燥により水分はＣａ （Ｏ
Ｈ）２基準で１０重量％以下にすることが、高密度焼結
体を得る上で望ましい。ざらにこれらの工程で得られた
乾燥物はボールミル、ヘンシェルミキサー等を用いて粉
砕することが、次に良い成形体を得る上で望ましい。When taking step (2), a drying step is required,
A commonly used dryer can be used. however,
When fossil fuel combustion gas is used for drying, it is necessary to suppress CO2 absorption to 5.0% by weight or less based on Ca (OH)2. Drying in an air atmosphere is desirable since there is no absorption of CO2. In addition, moisture is removed by drying as Ca (O
H) It is desirable that the content be 10% by weight or less based on 2 in order to obtain a high-density sintered body. In order to obtain the next best molded product, it is desirable to roughly pulverize the dried product obtained in these steps using a ball mill, Henschel mixer, or the like.
（２）および（３）の工程において成形は１ｔ／ｃｍ２
程度の加圧下で行なわれる。成形機は通常用いられるブ
リケットマシン等を用いることができる。In steps (2) and (3), the molding is 1t/cm2
It is carried out under moderate pressure. A commonly used briquette machine or the like can be used as the molding machine.
（３）の工程における仮焼は６００℃〜１ｏｏｏ’ｃの
間で行わなくてはならない。６００℃より低い温度では
仮焼の効果が小ざく、１０００℃より高温になると比表
面積の低下により、焼結性が低下する。ここで行なわれ
る仮焼は通常用いられる軽焼炉、ロータリーキルン等を
使用することができるが、この工程においてもＣＯ２の
吸収は可能な限り低く押えることが必要であり、ＣＯ２
分圧の低い、特に空気雰囲気下−で行うことが好ましい
。The calcination in step (3) must be performed at a temperature of 600°C to 100°C. At a temperature lower than 600°C, the effect of calcination is small, and at a temperature higher than 1000°C, the specific surface area decreases, resulting in a decrease in sinterability. The calcination carried out here can be carried out using a commonly used light furnace, rotary kiln, etc., but it is also necessary to suppress CO2 absorption as low as possible in this process.
It is preferable to carry out the reaction under a low partial pressure, particularly in an air atmosphere.
以上の様にして得られた濾過ケーキ、乾燥成形体、ある
いは仮焼成型体は次に１５００℃以上の温度、好ましく
は１６５０℃以上の温度で焼成されなければならない。The filter cake, dry molded body, or pre-fired molded body obtained as described above must then be fired at a temperature of 1500°C or higher, preferably 1650°C or higher.
この温度により、焼結が充分に進み、高高密度、大結晶
を有するカルシア焼結体が得られる。１５００℃より低
い温度ではカルシア結晶の発達が不十分であり、高い耐
消化性は得られない。焼成は通常マグネシアクリンカ−
を焼成する際に用いられる焼成炉を使用することができ
、たとえばロータリーキルン等が使用される。この場合
重油等の燃料を用いるため、炉内の雰囲気は空気雰囲気
と異なり、ＣＯ２およびＨ２０分圧の高い雰囲気となる
。この様な雰囲気下での焼成は本発明の組成とすること
で易焼結性となるため、何等差し支えないけれども、で
きればＣＯ２分圧の低い、空気雰囲気下で焼成すること
が好ましい。At this temperature, sintering progresses sufficiently, and a calcia sintered body having high density and large crystals is obtained. At temperatures lower than 1500°C, calcia crystals are insufficiently developed and high digestion resistance cannot be obtained. Firing is usually magnesia clinker
A firing furnace used for firing can be used, such as a rotary kiln. In this case, since fuel such as heavy oil is used, the atmosphere inside the furnace is different from an air atmosphere, and is an atmosphere with high partial pressures of CO2 and H20. Although there is no problem with firing in such an atmosphere because the composition of the present invention facilitates sintering, it is preferable to perform firing in an air atmosphere with a low CO2 partial pressure if possible.
本発明者らによればＣＯ２分圧の高い雰囲気下で焼成を
行うことにより、水酸化カルシウムケーキまたは成形体
の表面付近では比較的低温で起こるＣａＣＯｘの生成と
９００ ℃付近で起こるＣａＣＯｘの分解という２つの
過程を経る結果、得られるカルシア焼結体は気孔が多く
、高密度も低いものになることが見出された。また、こ
れらＣＯ２によるＣ
ａＣＯ３の生成は水酸化カルシウムを仮焼して、酸化カ
ルシウムにすることにより、大幅に低減できることも明
らかにされた。従ってＣＯ２分圧の高い雰囲気下で焼成
を行う場合は、上記工程のうち、（３）の仮焼成形工程
をとることが望ましい。According to the present inventors, by performing calcination in an atmosphere with a high CO2 partial pressure, the formation of CaCOx occurs at a relatively low temperature near the surface of the calcium hydroxide cake or molded body, and the decomposition of CaCOx occurs at around 900 °C. It has been found that as a result of the two processes, the resulting calcia sintered body has many pores and low density. It has also been revealed that the production of CaCO3 by CO2 can be significantly reduced by calcining calcium hydroxide to form calcium oxide. Therefore, when firing is performed in an atmosphere with a high CO2 partial pressure, it is desirable to perform the calcination forming step (3) among the above steps.
次に本発明の実施例および比較例を挙げ、具体的に説明
する。なお本発明における種々の測定法は下記の通りで
ある。Next, Examples and Comparative Examples of the present invention will be given and specifically explained. In addition, various measuring methods in the present invention are as follows.
１）嵩密度
日本学術撮興会第１２４委員会で提案された学振法２［
マグネシアクリンカ−見掛は気孔率、見掛は比重および
高比重の測定方法に準じて測定した。1) Bulk density JSPS proposed by the 124th Committee of the Japan Society for the Promotion of Science [2]
Magnesia clinker - Apparent was measured according to the method of measuring porosity, and apparent was measured according to the method of measuring specific gravity and high specific gravity.
２）平均結晶径
Ｆｕｌ１ｍａｎ法（Ｊ、ｏｆ、Ｍｅｔａｌｓ ４４７１
９５３） ニよった。すなわち研磨面を搬影した写真上
で任意に直線を引き、粒界によって切り取られる線分の
長さの平均値を１．５倍した値を平均粒径とした。なお
測定にあたってはクリンカー粒を５個以上選び、各々の
紙片につき、１００個以上の結晶を測定した。2) Average crystal diameter Fulman method (J, of, Metals 4471
953) Niyotta. That is, a straight line was arbitrarily drawn on a photograph of the polished surface, and the average value of the length of the line segment cut by the grain boundary was multiplied by 1.5 to determine the average grain size. In the measurement, five or more clinker grains were selected, and more than 100 crystals were measured for each piece of paper.
３）化学組成
日本学術撮興会第１２４委員会で提案された学振法１「
マグネシアクリンカ−の化学分析法」に準じて測定した
。3) Chemical composition The JSPS Law 1 proposed by the 124th Committee of the Japan Society for the Promotion of Science
It was measured according to the chemical analysis method for magnesia clinker.
４）重量増加率
耐消化性の目安として、２．ＯＯ〜４．４７ｍｍに分級
したカルシア焼結体を相対湿度６５％、気温２０℃の空
気中に２週間静置して重量増加を測定して、もとの重量
に対重る増加量を％で表示した。4) Weight increase rate As a guideline for digestion resistance, 2. The calcia sintered body classified into 0~4.47 mm was left standing in air at a relative humidity of 65% and a temperature of 20°C for two weeks, the weight increase was measured, and the weight increase was calculated as a percentage of the original weight. It was displayed in
５）水酸化カルシウム粒度
水スラリーを篩を用いて分級して、篩上に残った水酸化
カルシウムの重量から求めた。5) Calcium hydroxide particle size The water slurry was classified using a sieve, and the particle size was determined from the weight of calcium hydroxide remaining on the sieve.
よ厖■
実施例１〜３、比較例１〜４
生石灰を純水中６０℃の温水で消和した後に分級して、
第１表に示す化学組成および粒度を有する水酸化カルシ
ウムを１ｑだ。これにＡ Ｉ ２０３ Ｎ Ｚ ｒ Ｏ
２をスラリー中で所定量添加混合した。ここでＡｌ２Ｏ
３は高純度Ｔ−Ａ Ｉ ２０３’粉末、’；ｌ ｒ Ｏ
２は酢酸ジルコニル溶液（試薬）として添加混合した。Examples 1 to 3, Comparative Examples 1 to 4 Quicklime was slaked with pure water at 60°C and then classified.
1 q of calcium hydroxide having the chemical composition and particle size shown in Table 1. To this A I 203 N Z r O
A predetermined amount of 2 was added and mixed in the slurry. Here Al2O
3 is high purity T-A I 203'powder,'; l r O
2 was added and mixed as a zirconyl acetate solution (reagent).
得られた混合スラリーを濾過、乾燥、粉砕した後、Ｉｔ
／ｃｍ２の加圧下で成形した。これら成形体を破砕して
３．６６〜５． ｆ３６ｍｍの粒度に調整して、空気雰
囲気下で１６５０℃で焼成した。冷却して得られたカル
シア焼結体の物性を第２表に示す。After filtering, drying and pulverizing the obtained mixed slurry, It
It was molded under pressure of /cm2. These molded bodies are crushed and 3.66 to 5. The particle size was adjusted to f36 mm and fired at 1650° C. in an air atmosphere. Table 2 shows the physical properties of the calcia sintered body obtained by cooling.
第１表
ｉａｉ％
第２表
実施例４
焼成を１５５０℃で行う他は実施例１と同じ条件で実験
を行った。冷却して得られたカルシア焼結体の物性を第
３表に示す。Table 1 iai% Table 2 Example 4 An experiment was conducted under the same conditions as Example 1 except that the firing was performed at 1550°C. Table 3 shows the physical properties of the calcia sintered body obtained by cooling.
第３表
実施例５、比較例５
プロパンおよび酸素を燃料とする焼成炉を用いて、１７
００℃で焼成を行うこと、および組成の他は実施例１と
同じ条件で行った。冷却して１＠られたカルシア焼結体
の組成および物性を第４表に示す。Table 3 Example 5, Comparative Example 5 Using a firing furnace fueled by propane and oxygen, 17
The same conditions as in Example 1 were used except for firing at 00°C and the composition. Table 4 shows the composition and physical properties of the calcia sintered body after cooling.
Ｉ！！４表
実施例６
実施例１で用いた原料粉末を空気雰囲気下で、８００℃
で仮焼を行った後にｉ ｔ／ｃｍ ’の加圧下で成形し
て、得られた成形体を破砕して、３．３６〜５．６６ｍ
ｍの粒度に調整した後に焼成を行う他は実施例４と同じ
条件で行った。冷却して１ワられたカルシア焼結体の物
性を第５表に示す。I! ! Table 4 Example 6 The raw material powder used in Example 1 was heated to 800°C in an air atmosphere.
After calcination at
The process was carried out under the same conditions as in Example 4, except that the firing was performed after adjusting the particle size to m. Table 5 shows the physical properties of the calcia sintered body which was cooled and subjected to one-warming.
第５ａ ４・発明の効果
本発明により、化学組成がＣａＯ９７．５重Φ％以上の
高純度であり、かつ高密度が３．２０ｑ／ＣＣ以上であ
り、かつカルシア結晶の平均粒径が６０μｍ以上の耐消
化性に優れるカルシア焼結体が、Ａｌ２Ｏ３、ＺｒＯ２
を同時に、かつ微量混合して焼成するという比較的容易
な方法で得られる。実施例１で見られる様に相対湿度６
５％の空気中に放置しても、２週間後の重量増が０．１
３％と著しく低く、肉眼では何ら変化も観察されない。Part 5a 4. Effects of the Invention According to the present invention, the chemical composition is CaO97.5% by weight or more, high purity, the high density is 3.20q/CC or more, and the average grain size of calcia crystals is 60 μm or more. Calcia sintered body with excellent digestion resistance is used for Al2O3, ZrO2
It can be obtained by a relatively easy method of simultaneously mixing a small amount and firing. Relative humidity 6 as seen in Example 1
Even if left in 5% air, the weight increase after 2 weeks is 0.1
It is extremely low at 3%, and no change is observed with the naked eye.
従って、本発明品はカルシアを工業的に利用する際の大
ぎな支障であった耐消化性を大幅に改善し、また高密度
、純度ともに高く、耐スラグ性、機械的強度も期待され
、工業分野で充分活用できることが可能となった。Therefore, the product of the present invention has greatly improved the digestion resistance, which was a major hindrance when using calcia industrially, and is also expected to have high density and purity, slag resistance, and mechanical strength, and is expected to be suitable for industrial use. It has become possible to fully utilize it in the field.
第１図は所定量のＡ Ｉ ２０３ 、Ｚ ｒＱ２を含む
カルシア焼結体の各焼成温度におけるカルシア結晶の平
均粒子径を示すグラフ、第２図は同じ試料による各焼成
温度における嵩密度を示すグラフ、
第３図は実施例１のカルシア焼結体の研磨面の組織を示
す顕微鏡写真、
第４図は比較例１のカルシア焼結体の研磨面の組織を示
す顕微鏡写真である。
特許出願人 新日本化学工業株式会社
代理人 弁理士 小 松 秀 岳
代理人 弁理士 旭 宏
焼成温ＪＩ（℃）
ｙＰ１図
ォ３ｎ ’朔″
第４図 １吸９Figure 1 is a graph showing the average particle diameter of calcia crystals at each firing temperature of a calcia sintered body containing predetermined amounts of A I 203 and Z rQ2, and Figure 2 is a graph showing the bulk density of the same sample at each firing temperature. , FIG. 3 is a microphotograph showing the structure of the polished surface of the calcia sintered body of Example 1, and FIG. 4 is a microphotograph showing the structure of the polished surface of the calcia sintered body of Comparative Example 1. Patent Applicant Shin Nippon Chemical Industry Co., Ltd. Agent Patent Attorney Hide Komatsu Agent Patent Attorney Hiroshi Asahi Firing Temperature JI (℃) yP1 Figure 3n 'Saku'' Figure 4 1 Suction 9
Claims (8)
．５以上 Ａｌ＿２Ｏ＿３０．０５以上０．５以下 ＺｒＯ＿２０．１以上１．０以下 および残部が不可避の不純物から成り、か つ嵩密度が３．２０ｇ／ｃｃ以上であり、かつカルシア
結晶の平均粒径が６０μｍ以上であることを特徴とする
カルシア焼結体。(1) Composition is CaO97 expressed in weight% on scorching heat basis
．． 5 or more Al_2O_30.05 or more and 0.5 or less ZrO_20.1 or more and 1.0 or less and the remainder consisting of unavoidable impurities, and has a bulk density of 3.20 g/cc or more, and has an average grain size of calcia crystals of 60 μm or more A calcia sintered body characterized by:
体。(2) The calcia according to claim (1), which has a composition of CaO of 98.0 or more, exceeding Al_2O_30.1, and 0.3 or less of ZrO_20.1 or more, less than 0.5, expressed in weight percent based on scorching heat. Sintered body.
範囲第（１）項または第（２）項のいずれかに記載のカ
ルシア焼結体。(3) The calcia sintered body according to claim 1 or 2, which has a bulk density of 3.26 g/cc or more.
許請求の範囲第（１）〜（３）項のいずれかに記載のカ
ルシア焼結体。(4) The calcia sintered body according to any one of claims (1) to (3), wherein the average grain size of the calcia crystals is 80 μm or more.
つＣＯ＿２含有量がＣａ（ＯＨ）＿２基準で５．０重量
％以下の水酸化カルシウム （ｂ）Ａｌ＿２Ｏ＿３または熱分解してＡｌ＿２Ｏ＿３
となるアルミニウム化合物 （ｃ）ＺｒＯ＿２または熱分解してＺｒＯ＿２となるジ
ルコニウム化合物 を混合することにより、組成調整をした原料をそのまま
で、あるいは加圧して成形体とした後に、１５００℃以
上で焼成することを特徴とするカルシア焼結体の製造方
法。(5) Particles with a diameter of 44 μm or less, such that the composition, expressed in weight percent based on scorching heat, consists of CaO of 97.5 or more, Al_2O_3 of 0.05 or more, ZrO of 20.1 or more and 1.0 or less, and the balance being unavoidable impurities. Calcium hydroxide (b) Al_2O_3 or thermally decomposed Al_2O_3 with a CO_2 content of 98% by weight or more and a CO_2 content of 5.0% by weight or less based on Ca(OH)_2
By mixing an aluminum compound (c) ZrO_2 or a zirconium compound that thermally decomposes to become ZrO_2, the raw material whose composition has been adjusted is either as it is or pressurized to form a molded body, and then fired at 1500 ° C or higher. A method for producing a calcia sintered body, characterized by:
下で仮焼を行なった後に、加圧して成形体とする特許請
求の範囲第（５）項記載のカルシア焼結体の製造方法。(6) The method for producing a calcia sintered body according to claim (5), wherein the raw material whose composition has been adjusted is calcined at a temperature of 600° C. or more and 1000° C. or less, and then pressurized to form a compact.
６）項記載のカルシア焼結体の製造方法。(7) Claim No. 2, wherein the atmosphere during calcination is air.
6) The method for producing a calcia sintered body as described in item 6).
第５〜８項のいずれかに記載のカルシア焼結体の製造方
法。(8) The method for producing a calcia sintered body according to any one of claims 5 to 8, wherein the firing temperature is 1650°C or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61022975A JPS62182154A (en) | 1986-02-06 | 1986-02-06 | Calcia sintered body and manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61022975A JPS62182154A (en) | 1986-02-06 | 1986-02-06 | Calcia sintered body and manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62182154A true JPS62182154A (en) | 1987-08-10 |
| JPH0329020B2 JPH0329020B2 (en) | 1991-04-22 |
Family
ID=12097560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61022975A Granted JPS62182154A (en) | 1986-02-06 | 1986-02-06 | Calcia sintered body and manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62182154A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008267797A (en) * | 2007-03-28 | 2008-11-06 | Mitsubishi Heavy Ind Ltd | Metal melting crucible and its surface treatment method |
| JP2009243723A (en) * | 2008-03-28 | 2009-10-22 | Mitsubishi Heavy Ind Ltd | Crucible for melting metal and its manufacturing method |
| JP2011173737A (en) * | 2010-02-23 | 2011-09-08 | Mitsubishi Heavy Ind Ltd | Method for producing crucible for melting metal |
| JP2011174627A (en) * | 2010-02-23 | 2011-09-08 | Mitsubishi Heavy Ind Ltd | Crucible for melting metal |
-
1986
- 1986-02-06 JP JP61022975A patent/JPS62182154A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008267797A (en) * | 2007-03-28 | 2008-11-06 | Mitsubishi Heavy Ind Ltd | Metal melting crucible and its surface treatment method |
| JP2009243723A (en) * | 2008-03-28 | 2009-10-22 | Mitsubishi Heavy Ind Ltd | Crucible for melting metal and its manufacturing method |
| JP2011173737A (en) * | 2010-02-23 | 2011-09-08 | Mitsubishi Heavy Ind Ltd | Method for producing crucible for melting metal |
| JP2011174627A (en) * | 2010-02-23 | 2011-09-08 | Mitsubishi Heavy Ind Ltd | Crucible for melting metal |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0329020B2 (en) | 1991-04-22 |
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