JPS6283357A - Calcia-magnesia base refractory composition for purification - Google Patents
Calcia-magnesia base refractory composition for purificationInfo
- Publication number
- JPS6283357A JPS6283357A JP60224468A JP22446885A JPS6283357A JP S6283357 A JPS6283357 A JP S6283357A JP 60224468 A JP60224468 A JP 60224468A JP 22446885 A JP22446885 A JP 22446885A JP S6283357 A JPS6283357 A JP S6283357A
- Authority
- JP
- Japan
- Prior art keywords
- cao
- refining
- calcia
- mgo
- desulfurization
- 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.)
- Pending
Links
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims description 44
- 239000000395 magnesium oxide Substances 0.000 title claims description 32
- 239000000203 mixture Substances 0.000 title claims description 29
- 238000000746 purification Methods 0.000 title 1
- 238000007670 refining Methods 0.000 claims description 25
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 34
- 229910052751 metal Inorganic materials 0.000 description 26
- 239000002184 metal Substances 0.000 description 26
- 238000006477 desulfuration reaction Methods 0.000 description 21
- 230000023556 desulfurization Effects 0.000 description 21
- 239000000956 alloy Substances 0.000 description 17
- 229910045601 alloy Inorganic materials 0.000 description 17
- 239000000292 calcium oxide Substances 0.000 description 17
- 235000012255 calcium oxide Nutrition 0.000 description 17
- 230000000694 effects Effects 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000011575 calcium Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000011819 refractory material Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011822 basic refractory Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000011823 monolithic refractory Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
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】
［産業上の利用分野］
本発明は精錬用カルシア−マグネシア系耐火組成物に係
り、特に精錬時の脱硫能力が著しく高い精錬用カルシア
−マグネシア系耐火組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a calcia-magnesia-based refractory composition for refining, and particularly to a calcia-magnesia-based refractory composition for refining that has an extremely high desulfurization ability during refining.
［従来の技術］
一般に金属又は合金中に残留酸素及び硫黄が多いと、加
工性や機械的特性が低下することはよく知られている。[Prior Art] It is well known that if a metal or alloy contains a large amount of residual oxygen and sulfur, its workability and mechanical properties will generally deteriorate.
このため金属又は合金の精錬には、残留酸素及び硫黄を
十分に少なくすることが重要である。Therefore, in refining metals or alloys, it is important to sufficiently reduce residual oxygen and sulfur.
真空又はアルゴンガス雰囲気下での、精錬中の脱酸、脱
硫について、特公昭５４−８４９号、特公昭５４−２４
６８８及び特開昭５２−５８０１０号に、それぞれＣａ
ｂ（酸化カルシウム）含有率の高い塩基性耐火物で裏付
けされた溶解炉又は取鍋を用い、真空又はアルゴンガス
雰囲気中で溶湯中にアルミニウム（Ａｉ）またはその合
金を添加することを特徴とする脱酸、脱硫方法が提案さ
れている。この原理はＡｎの添加により耐火物中のＣａ
Ｏを還元し、還元生成物であるカルシウム（Ｃａ）によ
り溶湯中の硫黄（Ｓ）、酸素（０）を除去するものであ
る。Regarding deoxidation and desulfurization during refining under vacuum or argon gas atmosphere, Japanese Patent Publication No. 54-849, Japanese Patent Publication No. 54-24
688 and JP-A No. 52-58010, Ca
It is characterized by adding aluminum (Ai) or its alloy to the molten metal in a vacuum or argon gas atmosphere using a melting furnace or ladle supported by a basic refractory with a high b (calcium oxide) content. Deoxidation and desulfurization methods have been proposed. This principle is based on the addition of An to increase Ca in the refractory.
This method reduces O and removes sulfur (S) and oxygen (0) in the molten metal using calcium (Ca), which is a reduction product.
［発明が解決しようとする問題点］
上記従来の方法では、一応の脱酸、脱硫が可能であるが
、合金の精錬分野においては、より高い脱酸脱硫能が要
求されており、より優れた精錬技術の出現が望まれてい
る。[Problems to be Solved by the Invention] The conventional methods described above are capable of deoxidizing and desulfurizing to a certain extent, but in the field of alloy refining, higher deoxidizing and desulfurizing ability is required. It is hoped that refining technology will emerge.
［問題点を解決するための手段］
本発明は、上記従来法に比し、格段に優れた脱硫、脱酸
効果、特に脱硫効果を得ることができる耐火組成物を提
供するものであり、ＭｇＯを１５〜７５重量％含み、Ｓ
ｉ Ｏ２が０．５重量％以下であることを特徴とする
精錬用カルシア−マグネシア系耐火組成物を要旨とする
ものである。[Means for Solving the Problems] The present invention provides a refractory composition that can obtain much superior desulfurization and deoxidation effects, especially desulfurization effects, as compared to the above-mentioned conventional methods. Contains 15 to 75% by weight of S
The gist of the present invention is a calcia-magnesia refractory composition for refining, characterized in that iO2 is 0.5% by weight or less.
本出願人は、従来の技術の改良法として、ＭｇＯを１５
〜７５重量％含み、かつＣａＯを１５重量％以上含有す
るマグネシア質の耐火物をもって裏付けされた溶解炉又
は容器内の合金溶湯中に、真空又は非酸化性雰囲気でＡ
ｎを存在せしめる方法を見出し、先に出願した（特願昭
６０−９０５７１号、以下「先願」という）０本発明者
らは、この先願に基き、より優れた脱酸、脱硫効果を宥
する耐火組成物につき検討を重ねた結果、耐火組成物中
のＳ ｉ Ｏ２が金属又は合金の精錬に悪影響を及ぼす
ことを知見し、耐火物中の５ｆＯ２量の上限を規定し、
優れた作用効果を発揮し得るＣ ａ Ｏ−Ｍ ｇ Ｏ系
耐火物を見い出すことにより、本発明を完成させたもの
である。As an improvement over the prior art, the applicant has proposed that MgO
~75% by weight and in a molten alloy in a melting furnace or container supported by a magnesia refractory containing 15% by weight or more of CaO in a vacuum or non-oxidizing atmosphere.
Based on this earlier application, the present inventors discovered a method to make n exist and filed an earlier application (Japanese Patent Application No. 60-90571, hereinafter referred to as the "earlier application"). As a result of repeated studies on refractory compositions, it was discovered that S i O2 in refractory compositions has a negative effect on the refining of metals or alloys, and the upper limit of the amount of 5fO2 in refractories was stipulated.
The present invention was completed by discovering a CaO-MgO-based refractory that can exhibit excellent effects.
即ち、一般にＣａＯ−ＭｇＯ系耐火物例えばドロマイト
は多量の５ｉ０２を含有しており、高純度品であっても
、通常２重量％程度のＳ ｉ Ｏ２を含有している。こ
れに対して１本発明の精錬用カルシア−マグネシア系耐
火組成物は５ｉ０２を０．５重量％以下と大幅に低減さ
せたものである。That is, CaO-MgO refractories such as dolomite generally contain a large amount of 5i02, and even high-purity products usually contain about 2% by weight of S i O2. In contrast, the calcia-magnesia refractory composition for refining of the present invention has a significantly reduced 5i02 content of 0.5% by weight or less.
以下本発明の構成について詳細に説明する。The configuration of the present invention will be explained in detail below.
なお、以下において％は重量％を表わす。In addition, below, % represents weight %.
本発明の精錬用カルシア−マグネシア系耐火組成物は、
少なくとも精錬時に金属又は合金の溶湯と直接接触する
炉壁を主に構成するためのものであり、定形耐火物、不
定形耐火物、坩堝構成材、内張り用吹付は材のいずれに
も適用される。また溶湯中に添加するフラックスとして
用いることもできる。The calcia-magnesia-based refractory composition for refining of the present invention is
It is mainly used to construct the furnace wall that comes into direct contact with molten metal or alloy during refining, and spraying for shaped refractories, monolithic refractories, crucible constituent materials, and lining materials is applicable to all materials. . It can also be used as a flux added to molten metal.
本発明の精錬用カルシア−マグネシア系耐火組成物は、
ＭｇＯを１５〜７５％、５ｉＯ２０，５％以下のＣａＯ
系組成物である。以下に、本発明において、ＭｇＯ含有
量を１５〜７５％、Ｓ ｉ ０２含有量を０．５％以下
とした理由について説明する。The calcia-magnesia-based refractory composition for refining of the present invention is
MgO 15-75%, 5iO20, 5% or less CaO
It is a system composition. Below, in the present invention, the reason why the MgO content is set to 15 to 75% and the S i 02 content is set to 0.5% or less will be explained.
一般に、ＣａＯ質耐火物は、高温でも安定であり、各種
の反応性の高い合金溶湯の溶解に用いられていることは
周知である。また、ＣａＯ質耐火物が内張すされた容器
中の溶湯にＡ！；Ｌ及び／又はＡ１合金を添加すると、
ＡｌによってＣａＯが還元されＣａが生じ、脱酸、脱硫
反応が進行することも公知である。It is generally known that CaO refractories are stable even at high temperatures and are used for melting various highly reactive molten alloys. In addition, A! ; When L and/or A1 alloy is added,
It is also known that CaO is reduced by Al to produce Ca, and deoxidation and desulfurization reactions proceed.
ところが、下記反応式の如く、ＭｇＯとＣａＯとが共存
する炉壁においては、Ａｎ及び／又はＡ２合金を添加す
るとＣａの他にＭｇも生じる様になり、Ｃａ、Ｍｇが脱
酸、脱硫反応し、一層強力な脱酸、脱硫が行なわれる。However, as shown in the reaction formula below, in the furnace wall where MgO and CaO coexist, when An and/or A2 alloy is added, Mg is also produced in addition to Ca, and Ca and Mg undergo deoxidation and desulfurization reactions. , more powerful deoxidation and desulfurization are performed.
ｚＡ文＋３Ｍｇ０４Ａ見２０３＋３ＦｄｇｚＡ文＋３
Ｃａ Ｏ＋ Ａ ｌ ２０ ｇ ＋ ３ ＣａＭｇＯは
とりわけ２０〜６０％含まれる場合に、極めて強力な脱
硫反応が行なわれる。zA sentence + 3Mg04A look 203 + 3FdgzA sentence +3
Especially when CaO+A120g+3 CaMgO is contained in an amount of 20 to 60%, an extremely strong desulfurization reaction takes place.
Ｓ ｉ Ｏ２は溶湯に添加されたＡｉ及び／又はＡ１合
金によって還元され、
３ Ｓ ｆ Ｏ２＋ ４ Ａ ｌ→２Ａ交２０ｉ＋３ｓ
ｆとなり、Ａ ｌ ２０３クラスタを生じさせ、溶湯中
の酸素分圧を上昇させ、ひいては脱硫能も阻害する大き
な要因となる。従ってＳｉＯ２はできるだけ少なく、好
ましくは０．３％以下とするのが望ましい。S i O2 is reduced by Ai and/or A1 alloy added to the molten metal, 3 S f O2+ 4 A l → 2A cross 20i + 3s
f, which causes Al 203 clusters, increases the oxygen partial pressure in the molten metal, and becomes a major factor that inhibits the desulfurization ability. Therefore, it is desirable to keep the SiO2 content as low as possible, preferably 0.3% or less.
本発明のＣａ Ｏ−Ｍ ｇ Ｏ系耐火組成物のＣａＯは
、それ自体Ａｉによって還元され、Ｃａを生じさせると
共に、ＭｇＯと共存することによってＭｇＯの還元反応
を促進する。ＣａＯの好ましい含有率は、炉材全体の１
５％以上とりわけ４０％以上である。CaO in the CaO-MgO-based refractory composition of the present invention is itself reduced by Ai to generate Ca, and coexists with MgO to promote the reduction reaction of MgO. The preferred content rate of CaO is 1% of the entire furnace material.
It is 5% or more, especially 40% or more.
ＣａＯ含有率が４０％未満の場合には、耐火物中のＣａ
Ｏは他の酸化物と強固に結合しているため、ＣａＯの活
性が少なく、ＡｆＬにより還元されにくい、これに対し
、４０％以上のＣａｏを有する耐火物中のＣａＯは活性
が大でＡｉＬによってよく還元することができる。If the CaO content is less than 40%, Ca in the refractory
O is strongly bonded to other oxides, so CaO has low activity and is difficult to be reduced by AfL.On the other hand, CaO in refractories with CaO of 40% or more has high activity and is reduced by AiL. It can be returned well.
また、ＣａＯを４０％以上含む耐火物は、Ａｉ２０３や
５Ｌ０２等の酸化物と反応し易く、従って、溶湯中の酸
化物を吸収し、酸化物介在量を大幅に減少させる。また
ＣａＯを４０％以上含む耐火物はＣ，Ｔｉ、Ｚｒ等に対
する安定性が高いので、高温溶解が可能となる。Furthermore, refractories containing 40% or more of CaO tend to react with oxides such as Ai203 and 5L02, and therefore absorb oxides in the molten metal and significantly reduce the amount of oxides present. Furthermore, since refractories containing 40% or more of CaO have high stability against C, Ti, Zr, etc., high-temperature melting is possible.
なお、本発明において、Ｃａ Ｏ−Ｍ ｇ Ｏ系耐火物
組成物中には、ＣａＯ２，Ａ交２０３．Ｃ等が含有され
ていても良い、しかるに、これらの成分が含有されてい
る場合には、その含有量が合計で１５％以下とするべき
のが好ましい。In the present invention, the CaO-MgO-based refractory composition contains CaO2, A203. C and the like may be contained.However, when these components are contained, it is preferable that their total content should be 15% or less.
なお、本発明のＣａＯ−ＭｇＯ系耐火組成物中にＦｅＯ
又はＦｅ２Ｏ３のＦｅ酸化物が含有されていると、これ
らが精錬時に溶湯中に溶解し、溶湯を汚染することがあ
るため、Ｆｅ醜化物含有量はできるだけ少なくすること
が好ましい、Ｆｅ酸化物の含有量は好ましくは５％以下
、特に１〜２％あるいはそれ以下にするのが望ましい。In addition, FeO is contained in the CaO-MgO-based refractory composition of the present invention.
If Fe2O3 or other Fe oxides are contained, they may dissolve into the molten metal during refining and contaminate the molten metal. Therefore, it is preferable to reduce the Fe ugliness content as much as possible. The amount is preferably less than 5%, especially 1-2% or less.
また、本発明のカルシア−マグネシア系耐火組成物の形
態は多孔質であることが好ましい０本発明の組成物を多
孔質とすることにより、精錬時における組成物と溶湯と
の接触面積、即ち反応界面積が大きくなり、より脱硫、
脱酸効率が高められる。多孔質とした場合、その気孔率
は工０％以上、好ましくは１５％以上、特に好ましくは
２０％以上とするのが好ましい、多孔質とするには、酸
化もしくは昇華等により消失する性質の粉粒体を混入せ
しめれば良い、気孔の特に好ましい孔径は、平均で０．
５〜０．０１ｍｍ、とりわけ０．３〜０．０５ｍｍ程度
である。In addition, the form of the calcia-magnesia-based refractory composition of the present invention is preferably porous. By making the composition of the present invention porous, the contact area between the composition and the molten metal during refining, that is, the reaction The interfacial area becomes larger, resulting in better desulfurization and
Deoxidizing efficiency is increased. When made porous, the porosity is preferably 0% or more, preferably 15% or more, particularly preferably 20% or more. The particularly preferable pore size of the pores into which the particles can be mixed is 0.5 mm on average.
It is about 5 to 0.01 mm, especially about 0.3 to 0.05 mm.
このような本発明の精錬用Ｃａ Ｏ−Ｍ ｇ Ｏ耐火組
成物は、Ｆｅ基、Ｃｏ基、Ｎｉ基合金、その他あらゆる
金属又は合金の精錬に有効である。Such a Ca O-M g O refractory composition for refining of the present invention is effective for refining Fe-based, Co-based, Ni-based alloys, and all other metals or alloys.
［作用］
通常ノＣａ Ｏ−Ｍ ｇ Ｏ系耐火物は５ｉ０２含有量
が比較的高いため、精錬時に添加されたＡｎと５ｉ０２
が反応してＡ ｌ ２０ ａを生成し、溶湯を汚染する
と共にその酸素分圧を上昇させる。このため脱酸効果が
劣り、しかも脱硫作用にも悪影響を及ぼす。[Function] Normal CaO-MgO-based refractories have a relatively high 5i02 content, so the An added during refining and 5i02
reacts to produce Al 20 a, which contaminates the molten metal and increases its oxygen partial pressure. For this reason, the deoxidizing effect is poor, and the desulfurization effect is also adversely affected.
これに対し１本発明の精錬用ＣａＯ−ＭｇＯ系耐火組成
物はＳｉＯ２が極めて少ないため、Ｓ ｉ Ｏ２による
脱酸、脱硫効果の低下がなく、良好な精錬効果を得るこ
とができる。On the other hand, since the CaO-MgO refractory composition for refining of the present invention has extremely low SiO2, there is no deterioration in the deoxidation and desulfurization effects caused by SiO2, and a good refining effect can be obtained.
本発明の精錬用ＣａＯ−ＭｇＯ系耐火組成物で内張すさ
れた容器中にて、金属又は合金溶湯に真空又は非酸化性
雰囲気でＡｎを存在せしめて精錬を行なった場合、溶湯
中のＡｎの一部は、直接に、溶湯中の酸素と結合して脱
酸を行なうが。When refining is performed in a container lined with the CaO-MgO-based refractory composition for refining of the present invention in the presence of An in a molten metal or alloy in a vacuum or in a non-oxidizing atmosphere, the An in the molten metal is A part of it directly combines with oxygen in the molten metal to deoxidize it.
Ａｎの他の部分は耐火物表面のＭｇＯ１ＣａＯと反応し
て
２Ａ交＋３ Ｍ ｇ Ｏ＝ Ａ ｌ ２０３ ＋ ３
Ｍ ｇ２Ａｉ＋３ＣａＯ＋Ａ交２０ａ＋３ｃ＆となり、
Ｍｇ、ＣａとＡ ｌ ２０３が生じる。The other part of An reacts with MgO1CaO on the refractory surface to form 2A cross +3 M g O = A l 203 + 3
M g2Ai+3CaO+A cross 20a+3c&,
Mg, Ca and Al 203 are produced.
このＭｇ、Ｃａは脱酸、脱硫反応し、ＭｇＯｌＣａＯｌ
ＭｇＳ、ＣａＳとなる。These Mg and Ca undergo deoxidation and desulfurization reactions, and MgOlCaOl
They become MgS and CaS.
一方、ＡｆＬ２０３は、
Ａ ｌ ２０３ ＋ ３ Ｃａ Ｏ＋ ３ Ｃａ Ｏｍ
Ａ文２０３なる反応により３Ｃａｏ・Ａｊ１２０３
（以下Ｃ３Ａということがある。）を主体とするカルシ
ウムアルミネートを形成する。このＣ３Ａは溶湯の脱硫
能が高く、Ｃ３Ａによっても脱硫が進行する。On the other hand, AfL203 is A l 203 + 3 Ca O+ 3 Ca Om
3Cao・Aj1203 due to the reaction A sentence 203
(hereinafter sometimes referred to as C3A). This C3A has a high ability to desulfurize the molten metal, and desulfurization also progresses with C3A.
このように、Ａｉにより脱硫が、またＡｆＬの還〒性田
ζ上１１庄ｒト沃硅かＭａｒ、Ｃ＾−Ｃ，Ａにより脱酸
と脱硫が行なわれる。In this way, desulfurization is carried out by Al, and deoxidation and desulfurization are carried out by Iodine, Mar, C^-C, and A.
この反応は、極めて急速に進行し、例えばＡｆＬを溶湯
中に存在せしめた後、数分程度で脱硫、脱酸がほぼ完了
する。This reaction progresses extremely rapidly, and for example, desulfurization and deoxidation are almost completed in about a few minutes after AfL is made to exist in the molten metal.
また、時間の経過と共に、次第に溶湯中の窒素量が減少
してくる。これはＣａ等の蒸発（沸騰）等に伴ってＮも
溶湯から離脱するためである。この脱窒速度は、アルゴ
ン又は真空雰囲気下では、脱酸、脱硫の進行に従って著
しく向上する。Moreover, as time passes, the amount of nitrogen in the molten metal gradually decreases. This is because N also leaves the molten metal as Ca and the like evaporate (boil). This denitrification rate improves significantly under an argon or vacuum atmosphere as deoxidation and desulfurization progress.
［実施例］ 以下実施例及び比較例について説明する。[Example] Examples and comparative examples will be described below.
比較例１
一級試薬を原料として得られたＣａ０（Ｃａ０９８％以
上）坩堝内で第１表に示す組成の電解鉄に０．０３％程
度の硫黄成分になるように予めＦｅＳを添加した鉄５０
０ｇを５０ＫＨｚ高周波溶解炉にて溶解し、アルゴン雰
囲気下で、Ａ１合金を０．５％添加した。Comparative Example 1 Iron 50 was prepared by adding FeS to electrolytic iron having the composition shown in Table 1 in advance in a Ca0 (Ca0 98% or more) crucible obtained using a first-class reagent as a raw material so as to have a sulfur content of about 0.03%.
0g was melted in a 50KHz high frequency melting furnace, and 0.5% of A1 alloy was added under an argon atmosphere.
坩堝内の合金溶湯の硫黄含有量の経時変化を測定した。Changes in the sulfur content of the molten alloy in the crucible over time were measured.
その結果を第１図に示す。The results are shown in FIG.
第１表 （電解鉄組成）（％）
比較例２
ＣａＯ−４９％ＭｇＯ−２％Ｓ ｉ Ｏ２坩堝を用いて
行なったこと以外は、比較例１と同様の手順により実験
を行なった。その結果を第１図に示す。Table 1 (Electrolytic iron composition) (%) Comparative Example 2 An experiment was conducted in the same manner as in Comparative Example 1, except that a CaO-49%MgO-2%SiO2 crucible was used. The results are shown in FIG.
比較例３
ＣａＯ−５０％ＭｇＯ−０，６％５ ｆ Ｏ２坩堝を用
いて行ったこと以外は、比較例１と同様の手順により実
験を行った。その結果を第１図に示す。Comparative Example 3 An experiment was conducted in the same manner as in Comparative Example 1, except that a CaO-50% MgO-0.6% 5 f O2 crucible was used. The results are shown in FIG.
実施例１
一級試薬のみを原料とし、Ｓ ｉ ０２を実質的に含有
しないＣａｂ−５０％ＭｇＯ坩堝を用いて行なったこと
以外は、比較例１と同様にして実験を行なった。その結
果を第１図に示す。Example 1 An experiment was conducted in the same manner as in Comparative Example 1, except that only a first-class reagent was used as a raw material and a Cab-50% MgO crucible containing substantially no SiO2 was used. The results are shown in FIG.
第１図より、本発明の組成物によれば、比較例１．２，
３に比べ、硫黄含有量の少ない溶湯が速やかに得られる
ことが認められる。From FIG. 1, according to the composition of the present invention, Comparative Example 1.2,
It is recognized that a molten metal with a lower sulfur content can be obtained more quickly than in Example 3.
実施例２
一級試薬のみを原料とし、ＳｉＯ２を実質的に含有しな
いＣａＯＣａＯ−３Ｏ及びＣａＯ−５０％ＭｇＯの気孔
率を第２表の如く変えて、各々の組成物により製作され
た坩堝を用いて、比較例１と同様にして電解鉄の精錬を
行なった。Example 2 Using only a first-class reagent as a raw material, the porosity of CaOCaO-3O and CaO-50%MgO, which do not substantially contain SiO2, was changed as shown in Table 2, and crucibles made with each composition were used. , Electrolytic iron was refined in the same manner as in Comparative Example 1.
得られた溶湯中のＳ含有量の分析結果を第２表に示す。Table 2 shows the analysis results of the S content in the obtained molten metal.
第２表 Ｓ含有量（ｐｐｍ）
第２表より、カルシア−マグネシア系耐火組成物が気孔
質の高い多孔質であると脱硫効果がより向上することが
明らかである。Table 2 S content (ppm) From Table 2, it is clear that the desulfurization effect is further improved when the calcia-magnesia-based refractory composition is highly porous.
［効果］
以上詳述した通り、本発明の精錬用カルシア−マグネシ
ア系耐火組成物は、ＭｇＯを１５〜７５重量％含み、Ｓ
ｉ Ｏ２が０．５重量％以下のカルシア系組成物であ
って、Ｓ ｉ ０２による悪影響が解消され、ＭｇＯ，
ＣａＯによる優れた脱硫、脱酸、脱窒効果により金属又
は合金を良好に精錬することが可能とされる０本発明の
カルシア−マグネシア系耐火組成物をもって精錬を行な
うことにより、０、Ｎ、Ｓが極めて少なく、クリープ強
度、耐熱性、靭性、溶接性、鍛造性等の緒特性に介在さ
れる酸化物も殆ど無い。[Effect] As detailed above, the calcia-magnesia-based refractory composition for refining of the present invention contains 15 to 75% by weight of MgO and S
A calcia-based composition containing iO2 of 0.5% by weight or less, which eliminates the adverse effects of S iO2 and contains MgO,
By refining with the calcia-magnesia-based refractory composition of the present invention, which makes it possible to satisfactorily refine metals or alloys due to the excellent desulfurization, deoxidation, and denitrification effects of CaO, O, N, S There are very few oxides that interfere with properties such as creep strength, heat resistance, toughness, weldability, and forgeability.
第１図は実施例１、比較例１．２及び３により得られた
坩堝材質による溶湯のＳ含有量の経時変化の測定結果を
示すグラフである。FIG. 1 is a graph showing the measurement results of the change in S content of the molten metal with time depending on the crucible material obtained in Example 1 and Comparative Examples 1.2 and 3.
Claims (1)
精錬用カルシア−マグネシア系耐火組成物。(1) A calcia-magnesia-based refractory composition for refining, which contains 15 to 75% by weight of MgO and contains 0.5% by weight or less of SiO_2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60224468A JPS6283357A (en) | 1985-10-08 | 1985-10-08 | Calcia-magnesia base refractory composition for purification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60224468A JPS6283357A (en) | 1985-10-08 | 1985-10-08 | Calcia-magnesia base refractory composition for purification |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6283357A true JPS6283357A (en) | 1987-04-16 |
Family
ID=16814263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60224468A Pending JPS6283357A (en) | 1985-10-08 | 1985-10-08 | Calcia-magnesia base refractory composition for purification |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6283357A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5874564A (en) * | 1981-10-27 | 1983-05-06 | 黒崎窯業株式会社 | Magnesia lime refractories |
| JPS6054969A (en) * | 1983-09-02 | 1985-03-29 | 川崎製鉄株式会社 | Lining method of converter lining refractories |
-
1985
- 1985-10-08 JP JP60224468A patent/JPS6283357A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5874564A (en) * | 1981-10-27 | 1983-05-06 | 黒崎窯業株式会社 | Magnesia lime refractories |
| JPS6054969A (en) * | 1983-09-02 | 1985-03-29 | 川崎製鉄株式会社 | Lining method of converter lining refractories |
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