JP2983560B2 - Magnesia clinker - Google Patents
Magnesia clinkerInfo
- Publication number
- JP2983560B2 JP2983560B2 JP1330491A JP33049189A JP2983560B2 JP 2983560 B2 JP2983560 B2 JP 2983560B2 JP 1330491 A JP1330491 A JP 1330491A JP 33049189 A JP33049189 A JP 33049189A JP 2983560 B2 JP2983560 B2 JP 2983560B2
- Authority
- JP
- Japan
- Prior art keywords
- magnesia
- slaking
- clinker
- weight
- magnesia clinker
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims description 66
- 239000000395 magnesium oxide Substances 0.000 title claims description 33
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 229910052596 spinel Inorganic materials 0.000 description 7
- 239000011029 spinel Substances 0.000 description 7
- 150000004645 aluminates Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000011822 basic refractory Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- -1 aluminum organic acid Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VXYADVIJALMOEQ-UHFFFAOYSA-K tris(lactato)aluminium Chemical compound CC(O)C(=O)O[Al](OC(=O)C(C)O)OC(=O)C(C)O VXYADVIJALMOEQ-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は塩基性耐火物に用いられるマグネシアクリン
カーに関し、特に耐スレーキング特性に優れたマグネシ
アクリンカーに関する。Description: TECHNICAL FIELD The present invention relates to a magnesia clinker used for basic refractories, and more particularly to a magnesia clinker excellent in anti-slaking characteristics.
製鋼容器用塩基性耐火物に使用されるマグネシアクリ
ンカーは耐火性に富み、かつスラグに対する反応性の少
ない材料として多用されている。Magnesia clinker used for basic refractories for steelmaking vessels is widely used as a material having high fire resistance and low reactivity with slag.
〔発明が解決しようとする課題〕 このマグネシアは反面、熱膨脹が大きいことやスラグ
浸透の深いことゝ共にスレーキングを起こしやすい欠点
を有している。[Problems to be Solved by the Invention] On the other hand, magnesia has disadvantages that slaking is apt to occur in both large thermal expansion and deep slag penetration.
頻度の低いマグネシアクリンカーが使用されている場
合には不純物として存在するSiO2などの成分がクリンカ
ー製造時にペリクレス粒界に析出し、これがマグネシア
のスレーキングを防止していた。When a low-frequency magnesia clinker was used, components such as SiO 2 existing as impurities precipitated at the pericles grain boundaries during clinker production, which prevented magnesia slaking.
しかし、近年塩基性耐火物がさらに高耐用性を要求さ
れたり、高清浄鋼用の耐火物として利用されるようにな
り、高純度のマグネシアクリンカーが使用されるように
なってきた。不純物の少ないマグネシアクリンカーでは
従来自然に具備していた耐スレーキング性が低下し、キ
ャスタブルなどの水を使用する不定形耐火物としては使
用できないようになってきた。However, in recent years, basic refractories have been required to have higher durability or have been used as refractories for high-purity steel, and high-purity magnesia clinkers have been used. A magnesia clinker having a small amount of impurities has a reduced natural anti-slaking property and cannot be used as an amorphous refractory such as castable, which uses water.
したがって、高純度マグネシアクリンカーにおいて耐
スレーキング性の高い材料が要求されているのである。Therefore, there is a demand for a high-purity magnesia clinker with a material having high anti-slaking properties.
本発明者らは種々のマグネシアクリンカーについて検
討した結果、耐スレーキング性を持たせるためにMgO100
重量部に対してAl2O3を0.5〜10重量部、CaOを0.5〜５重
量部含有し、そのCaOおよびAl2O3はアルミン酸カルシウ
ムを生成し、主としてペリクレス粒界に存在するマグネ
シアクリンカーを得ることにより本発明を完成させたも
のである。The present inventors have studied various magnesia clinkers and found that MgO100
0.5 to 10 parts by weight of Al 2 O 3 and 0.5 to 5 parts by weight of CaO based on parts by weight, the CaO and Al 2 O 3 generating calcium aluminate, and a magnesia clinker mainly present at the pericles grain boundary Thus, the present invention has been completed.
本発明のマグネシアクリンカーにおいてはマグネシア
質原料にアルミナ質原料を添加するが、そこにCaO成分
が存在せずMgOのみであると、Al2O3はMgOと反応してMgO
リッチのスピネルを生成する。このMgOリッチのスピネ
ルではたとえそれがペリクレス粒界に生成してもそれ自
身がスレーキングを起こすため、クリンカーの耐スレー
キング性能は向上しない。In the magnesia clinker of the present invention, an alumina material is added to the magnesia material, but if there is no CaO component and only MgO, Al 2 O 3 reacts with MgO and MgO
Produces a rich spinel. This MgO-rich spinel does not improve the clinker's anti-slaking performance, because even if it forms at the pericles grain boundaries, it itself causes slaking.
しかし、CaOが共存すると、Al2O3は優先的にCaOと反
応して、3CaO・Al2O3やCaO・Al2O3のようなアルミン酸
塩を生成する。このアルミン酸塩は水と接触してもスレ
ーキングを起こさず、したがってそれがペリクレス粒界
に生成すればMgOのスレーキングを防止する作用があ
る。However, when CaO coexists, Al 2 O 3 preferentially reacts with CaO to produce aluminates such as 3CaO.Al 2 O 3 and CaO.Al 2 O 3 . This aluminate does not cause slaking even when it comes into contact with water, and therefore has the effect of preventing MgO from slaking if it forms at the pericles grain boundaries.
また、スピネルが生成する場合はその生成時の体積膨
脹のためクリンカーが密になりにくいが、アルミン酸塩
の生成の場合には密なクリンカーとなる利点もある。In addition, when spinel is formed, clinker is hardly dense due to volume expansion at the time of generation, but there is an advantage that dense clinker is formed when aluminate is generated.
本発明で使用されるマグネシア質原料は海水中のMg分
を沈澱させた水酸化マグネシウムやマグネサイト鉱石や
その仮焼物などでMg（OH）２やMgOあるいはMgCO3の組成
を持つ通常の原料でなるべく高純度のものが望ましい。
不純物のSiO2およびFe2O3はなるべく少ない方が好まし
い。The magnesia raw material used in the present invention is a normal raw material having a composition of Mg (OH) 2 , MgO or MgCO 3 such as magnesium hydroxide or magnesite ore or a calcined product thereof in which Mg content in seawater is precipitated. It is desirable to have high purity as possible.
It is preferable that the impurities SiO 2 and Fe 2 O 3 be as small as possible.
CaOはMgO100重量部に対して0.5〜５重量部で、通常は
マグネシア質原料に含まれているが、その量が少ない場
合は水酸化カルシウム、酸化カルシウム、炭酸カルシウ
ムなどの形で添加する。その量が0.5重量部以下ではア
ルミン酸塩の生成が少なく耐スレーキング性に劣り、５
重量部以上では耐食性が低下する。CaO is 0.5 to 5 parts by weight with respect to 100 parts by weight of MgO and is usually contained in the magnesia raw material, but when the amount is small, it is added in the form of calcium hydroxide, calcium oxide, calcium carbonate or the like. When the amount is 0.5 part by weight or less, the formation of aluminate is small and the anti-slaking property is poor.
If the amount is more than the weight part, the corrosion resistance is reduced.
アルミナ質原料の添加量はMgO100重量部に対してAl2O
3として0.5〜10重量部であり、水酸化アルミニウム、ア
ルミナゾル、炭酸アルミニウム、有機酸アルミニウムな
どの形で添加する。Al2O3の量が0.5重量部以下ではアル
ミン酸塩の生成が少なく耐スレーキング性に劣り、10重
量部以上ではスピネルが生成して耐スレーキング性能が
さほど向上しないばかりか密なクリンカーができにく
い。The amount of the alumina raw material added is 100 parts by weight of MgO and Al 2 O
3 is 0.5 to 10 parts by weight, and is added in the form of aluminum hydroxide, alumina sol, aluminum carbonate, aluminum organic acid or the like. When the amount of Al 2 O 3 is 0.5 parts by weight or less, the formation of aluminate is small and the anti-slaking property is inferior. .
本発明のマグネシアクリンカーの製造方法は通常のク
リンカーの製造方法と同様であり、原料混合物を水を加
えてスラリーとするか、ペレットに成形するかしてロー
タリーキルンなどで温度1800〜2000℃で焼成して製造す
る。本発明のマグネシアクリンカーにおいては製造時に
原料が溶融するとスピネルを生成し易すくなるので焼結
法により製造することが好ましい。The method for producing the magnesia clinker of the present invention is the same as the ordinary method for producing clinker, and the raw material mixture is made into a slurry by adding water, or formed into pellets or fired at a temperature of 1800 to 2000 ° C. in a rotary kiln or the like. Manufacturing. The magnesia clinker of the present invention is preferably manufactured by a sintering method because the melting of the raw material during the manufacture makes it easier to generate spinel.
第１表に示す原料配合をペレツトに成形後1800℃で焼
成してクリンカーを得た。マグネシア源としては工業用
水酸化マグネシウム（CaOとして約１％を含む）および
試薬級水酸化マグネシウム（CaOはほとんど含まず）を
用いた。アルミナ源としては水酸化アルミニウム、アル
ミナゾルおよび乳酸アルミニウムを用いた。The raw material composition shown in Table 1 was formed into a pellet and fired at 1800 ° C. to obtain clinker. As the magnesia source, industrial magnesium hydroxide (containing about 1% as CaO) and reagent grade magnesium hydroxide (containing almost no CaO) were used. As the alumina source, aluminum hydroxide, alumina sol and aluminum lactate were used.
製造したマグネシアクリンカーの成分比、物性および
耐スレーキング性を測定し、その結果も同じく第１表に
示す。なお、耐スレーキング性は学振法４マグネシアク
リンカーの消化試験方法によりクリンカーの粉化率を測
定して表わした。The composition ratio, physical properties and anti-slaking property of the produced magnesia clinker were measured, and the results are also shown in Table 1. In addition, the slaking resistance was represented by measuring the powdering rate of clinker by the digestion test method of Magnesia Clinker, Gakushin Method 4.
実施例の試料のEPMA観測の結果はいずれのクリンカー
もCaおよびAlはペリクレス粒界に見られ、Mgは粒界には
観測されなかった。これはアルミン酸カルシウムがペリ
クレス粒界に生成され、スピネルの生成はないことを示
している。一方、カルシウム成分のほとんどない比較例
２では粒界にスピネルが生成している。また、カルシウ
ム成分は存在してもアルミナ成分の多い比較例３ではス
ピネルが偏在し、その体積膨脹による空 隙が散見された。As a result of the EPMA observation of the sample of the example, Ca and Al were found at the pericles grain boundary and Mg was not observed at the grain boundary in each clinker. This indicates that calcium aluminate was formed at the pericles grain boundary and no spinel was formed. On the other hand, in Comparative Example 2 having almost no calcium component, spinel was formed at the grain boundary. Further, in Comparative Example 3 in which the calcium component was present but the alumina component was large, the spinels were unevenly distributed, and the volume was expanded due to the volume expansion. Gaps were scattered.
耐スレーキング特性も実施例のものは優れており、特
に実施例４のものが優れていた。これに対してマグネシ
アのみのもの（比較例１）はスレーキングを起こし、ア
ルミナを添加してもカルシウム成分のないもの（比較例
２）ではスレーキングの防止は不可能であった。また、
スピネルが偏在して空隙率の高いもの（比較例３）でも
スレーキングの防止は不可能であった。The anti-slaking property of the example was also excellent, and the anti-slaking property of the example 4 was particularly excellent. On the other hand, in the case of magnesia alone (Comparative Example 1), slaking was caused, and even in the case where alumina was added, slaking could not be prevented in the case of no calcium component (Comparative Example 2). Also,
Even if the spinel was unevenly distributed and the porosity was high (Comparative Example 3), it was impossible to prevent slaking.
このように本発明のアルミナ成分と酸化カルシウム成
分を共に含有するマグネシアクリンカーではペリクレス
粒界にアルミン酸カルシウムを生成させることによりス
レーキングの防止が可能となった。As described above, in the magnesia clinker containing both the alumina component and the calcium oxide component of the present invention, slaking can be prevented by forming calcium aluminate at the pericles grain boundaries.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C04B 35/00 - 35/22 ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. 6 , DB name) C04B 35/00-35/22
Claims (1)
部、CaOを0.5〜５重量部含有し、CaOおよびAl2O3はアル
ミン酸カルシウムを生成し、主としてペリクレス粒界に
存在する構造を有するマグネシアクリンカー。(1) 0.5 to 10 parts by weight of Al 2 O 3 and 0.5 to 5 parts by weight of CaO based on 100 parts by weight of MgO, CaO and Al 2 O 3 form calcium aluminate, Magnesia clinker having a structure existing in
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1330491A JP2983560B2 (en) | 1989-12-20 | 1989-12-20 | Magnesia clinker |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1330491A JP2983560B2 (en) | 1989-12-20 | 1989-12-20 | Magnesia clinker |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03193661A JPH03193661A (en) | 1991-08-23 |
| JP2983560B2 true JP2983560B2 (en) | 1999-11-29 |
Family
ID=18233220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1330491A Expired - Fee Related JP2983560B2 (en) | 1989-12-20 | 1989-12-20 | Magnesia clinker |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2983560B2 (en) |
-
1989
- 1989-12-20 JP JP1330491A patent/JP2983560B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03193661A (en) | 1991-08-23 |
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