JPS5842710A - Desulfurizer for blowing of molten iron - Google Patents

Desulfurizer for blowing of molten iron

Info

Publication number
JPS5842710A
JPS5842710A JP14014881A JP14014881A JPS5842710A JP S5842710 A JPS5842710 A JP S5842710A JP 14014881 A JP14014881 A JP 14014881A JP 14014881 A JP14014881 A JP 14014881A JP S5842710 A JPS5842710 A JP S5842710A
Authority
JP
Japan
Prior art keywords
weight
desulfurization
quicklime
parts
particle size
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
Application number
JP14014881A
Other languages
Japanese (ja)
Inventor
Toshihiko Wakayama
利彦 若山
Shuichi Ito
秀一 伊藤
Katsunori Tsutsumi
堤　勝則
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ibiden Co Ltd
Ibigawa Electric Industry Co Ltd
Original Assignee
Ibiden Co Ltd
Ibigawa Electric Industry Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ibiden Co Ltd, Ibigawa Electric Industry Co Ltd filed Critical Ibiden Co Ltd
Priority to JP14014881A priority Critical patent/JPS5842710A/en
Publication of JPS5842710A publication Critical patent/JPS5842710A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C1/00—Refining of pig-iron; Cast iron
    • C21C1/02—Dephosphorising or desulfurising
    • C21C1/025—Agents used for dephosphorising or desulfurising

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)

Abstract

PURPOSE:To provide a desulfurizer for blowing of molten iron which improves the efficiency of desulfurization reaction at a low cost by consisting the same of calcium carbide and quicklime of specified grain size distributions and compounding the same with prescribed contents of fluorite, sodium fluoride, soda ash, cryolite, etc. CONSTITUTION:A desulfurizer for molten iron consisting of 20-65pts.wt. calcium carbide, 75-30pts.wt. quicklime, 1-10pts.wt. fluorite, 0.5-5pts.wt. >=1 kind among sodium fluoride, soda ash, cryolite, and if necessary 5-15pts.wt. alumina. In the compsn. of said desulfurizer, >=70wt% a calcium carbide is regulated to <=74mu grain sizes and >=40wt% quicklime to 0.2-1mm. grain sizes. The desulfurizer provides a working effect upon the compounded quicklime by the synergistic effect of the additive components and improves the efficiency of desulfurization reaction.

Description

【発明の詳細な説明】 本発明は溶銑の吹込用脱硫剤に関する。[Detailed description of the invention] The present invention relates to a desulfurization agent for blowing hot metal.

溶銑の脱硫に関しては古くから広く研究が行なわれてお
り、一般に脱硫剤としては炭酸ナトリウム、水酸化ナト
リウムなどのナトリウム化合物、または力／Ｉ／Ｖウム
カーバイド、カルシウムシアナミド、生石灰などのカル
シウム化合物、およびカルシウム、マグネシウム金属の
単体、ま九はこれらの組み合わせのものがあり、必要と
する脱硫程度や脱硫設備に応じて選択されている。Desulfurization of hot metal has been extensively researched for a long time, and desulfurization agents generally include sodium compounds such as sodium carbonate and sodium hydroxide, or calcium compounds such as I/V um carbide, calcium cyanamide, and quicklime. There are single calcium and magnesium metals, and combinations of these metals, which are selected depending on the required degree of desulfurization and desulfurization equipment.

また、溶銑を脱硫処理する方法としては粒状脱硫剤を用
いるインペラー攪拌法、上吹あるいは底吹ガス攪拌法、
揺動取鍋法、回転ドラム法および粉状脱硫剤を用いる粉
末吹込法が古くから知られている。In addition, methods for desulfurizing hot metal include an impeller stirring method using a granular desulfurizing agent, a top blowing or bottom blowing gas stirring method,
The rocking ladle method, the rotating drum method and the powder blowing method using powdered desulfurization agents have been known for a long time.

現状では、大量の溶銑を短時間に脱硫処理できるなどの
理由からカルシウムカーバイド、生石灰を主体とする脱
硫剤を用いた粉末吹込法が広く採用されている。しかし
ながら、粉末吹込法は溶銑内下部に浸漬したフンスパイ
プを通じて窒素ガスなどの搬送ガスと共に溶銑内へ吹き
込まれた粉状脱硫剤の一部は溶銑中の硫黄と反応するが
、大部分は未反応な状態で溶銑表面へ浮上するという大
きな問題を有している。そのため力ｌＬ／Ｖウムヵ−バ
イトを主成分とする脱硫剤ではカルシウムカーバイドの
脱硫反応効率がわずか２　Ｇ−８０％であり、脱硫処理
コストが高くなるという欠点があった。Currently, the powder injection method using desulfurization agents mainly composed of calcium carbide and quicklime is widely adopted because it can desulfurize a large amount of hot metal in a short time. However, in the powder injection method, part of the powdered desulfurization agent that is blown into the hot metal together with a carrier gas such as nitrogen gas through a pipe immersed in the lower part of the hot metal reacts with the sulfur in the hot metal, but the majority remains unreacted. This poses a serious problem in that it floats to the surface of the hot metal. Therefore, a desulfurization agent containing carbide as a main component has a drawback that the desulfurization reaction efficiency of calcium carbide is only 2 G-80%, and the cost of desulfurization treatment is high.

また生石灰を主成分とする脱硫剤では生石灰の脱硫反応
効率が８〜１０％　と非常に低く、大量の脱硫剤を吹き
込まなければならないという欠点があった。Furthermore, desulfurization agents whose main component is quicklime have a very low desulfurization reaction efficiency of 8 to 10%, and have the disadvantage that a large amount of desulfurization agent must be blown into the desulfurization agent.

従って、前述の如きカルシウムカーバイド、生石灰を主
成分とする脱硫剤が従来種々提案されてきた０例えば、
特開昭４８−７９７１８号公報に見られる如く脱硫処理
中カルシウムカーバイドが酸化、窒化してブロッキング
を起し、脱硫反応効率が低下することを防ぐために、カ
ルシウムカーｌ＜イドに生石灰と石灰石および弗化ナト
リウム、炭酸ナトリウム、珪弗化ナトリウムから選ばれ
るナトリウム化合物を混合した脱硫剤が提案されている
。Therefore, various desulfurization agents mainly composed of calcium carbide and quicklime as mentioned above have been proposed.
As seen in JP-A No. 48-79718, in order to prevent calcium carbide from oxidizing and nitriding during desulfurization treatment, causing blocking and reducing the desulfurization reaction efficiency, quicklime, limestone, and fluoride are added to calcium carbide. A desulfurizing agent containing a mixture of sodium compounds selected from sodium chloride, sodium carbonate, and sodium silicofluoride has been proposed.

また、特開昭５５−４１９１２号公報に見られる如く、
力μシウムカーバイドの脱硫反応効率を高めると共に脱
硫剤コストの低減をはかるために、カルシウムカーバイ
ドと酸化力Ａｓｓ／ウムー１脚酸力〃Ｖウムおよび次素
材から選ばれた１種以上とを含有しテナル脱硫主剤ニ対
シテ、ＭｇＦｔ　、ＬｉＦ、ＮａＦ。Also, as seen in Japanese Patent Application Laid-Open No. 55-41912,
In order to increase the desulfurization reaction efficiency of μsium carbide and reduce the cost of the desulfurizing agent, it contains calcium carbide, oxidizing power Ass/Umu monopod acid power Vium, and one or more selected from the following materials. Tenal desulfurization main agents: MgFt, LiF, NaF.

ＫＦ、Ｎａｚ８ｉＦｓの中から選ばれた何れ力ｓ１種ま
たは２種以上を添加してなる脱硫剤も提案されている。A desulfurizing agent has also been proposed in which one or more selected from KF and Naz8iFs are added.

しかしながら、これら二つの従来の提案は何れも力ｆｉ
／Ｖウムカーバイドの脱硫反応効率の向上および脱硫剤
コストの低減に対してはある程度効果を奏しているが、
まだ十分に満足な効果を得るまでには至っていない。However, both of these two conventional proposals have no power
Although it has been effective to some extent in improving the desulfurization reaction efficiency of /V umium carbide and reducing the cost of desulfurization agent,
It has not yet been possible to obtain a sufficiently satisfactory effect.

本発明者等は力〜シウムカーバイドと生石灰と蛍石と弗
化すＦリウムとから成る脱硫剤は著しく良好な脱硫効果
が得られることを知見し、特願昭５５−１７１９０７号
および特願昭５６−６４５７０号の特許出願した。しか
し、この脱硫剤はインペラー攪拌脱硫において脱硫剤の
一着を防止するために脱硫剤全体の粒度分布が粗くなっ
ており吹込脱硫を採用し九場合には前記脱硫剤の脱硫能
力を十分に発揮させることができなかった。The present inventors have discovered that a desulfurizing agent consisting of sium carbide, quicklime, fluorite, and fluorinated Fium has an extremely good desulfurizing effect. -A patent application No. 64570 was filed. However, this desulfurization agent has a coarse particle size distribution in order to prevent the desulfurization agent from sticking during impeller agitation desulfurization. I couldn't let it go.

本発明紘、これらの欠点を解決することを目的とし、カ
ルシウムカーバイドに生石灰と蛍石と弗化ソーダ、ソー
ダ灰、氷晶石の何れかｌｌｉまたは２種以上とを配合す
ることにより、脱硫剤の脱硫反応効率を著しく高め経済
的に有利な溶銑の吹込用脱硫剤を提供するものである。The present invention aims to solve these drawbacks, and by blending calcium carbide with quicklime, fluorite, and any one or more of sodium fluoride, soda ash, and cryolite, a desulfurizing agent is produced. The object of the present invention is to provide an economically advantageous desulfurization agent for blowing hot metal that significantly increases the desulfurization reaction efficiency.

すなわち、本発明の脱硫剤バカルシウムカーバイド２０
〜６５重量部と生石灰７５〜８０重量部と蛍石１〜１０
重量部と弗化ソーダ、ソーダ灰、氷晶石の何れか１ｌｉ
ｔたは２種以上０．５〜６重量部とから主として成る総
重量が１００重量部である溶銑の脱硫剤であって、前記
力Ａ１５／ウムカーバイドの７０重量弧以上が７４．１
以下の粒径であり、前記生石灰の４０重量襲以上が０．
２〜１ｍの粒径であることを特徴とする。That is, the desulfurization agent bacalcium carbide 20 of the present invention
~65 parts by weight, 75-80 parts by weight of quicklime, and 1-10 parts of fluorite
Part by weight and 1 liter of sodium fluoride, soda ash, or cryolite
A desulfurizing agent for hot metal whose total weight is 100 parts by weight mainly consists of 0.5 to 6 parts by weight of two or more kinds, wherein the force A15/70 weight arc or more of um carbide is 74.1
The particle size is as follows, and the quicklime has a weight ratio of 40% or more.
It is characterized by a particle size of 2 to 1 m.

以下、本発明の脱硫剤を詳細に説明する。Hereinafter, the desulfurizing agent of the present invention will be explained in detail.

脱硫剤の脱硫反応効率を向上させる九めに蛍石に弗化ソ
ーダ、ソーダ灰、氷晶石を追加して脱硫剤に配合する。Ninth, to improve the desulfurization reaction efficiency of the desulfurization agent, add sodium fluoride, soda ash, and cryolite to fluorite and mix it into the desulfurization agent.

弗化ソーダ、ソーダ灰、氷晶石は蛍石と共存させて使用
すると極めて少量の添加で脱硫反応効率が著しく上昇す
るが、弗イヒソーダ、ソーダ灰、ンに晶石を蛍石と置き
換えて単独で窮１用しても著しい効果はみられない。When sodium fluoride, soda ash, and cryolite are used together with fluorite, the desulfurization reaction efficiency increases markedly with the addition of a very small amount. No significant effect was observed even after repeated use.

それ故、脱硫反応効率の著しい上昇は弗イヒソー　　ダ
、ソーダ灰、氷晶石と蛍石との相乗作用によるものと考
えられる。蛍石、弗イヒソーダ、ソーダ灰、氷晶石は未
反応な状態で溶銑上へ浮上した力〜シウムカーバイドが
溶銑上の雰囲気により酸イヒされ生成した生石灰および
脱硫型自身に配合されている生石灰に対して作用効果を
発揮する。蛍石によって生石灰表層部の融点が降下して
表面力！活性になり、弗化ソーダ、ソーダ灰、氷晶石と
の反応カニ促進される。ここで弗化ソーダ、ソーダ灰、
氷晶石は融剤として作用するば力為りでなく、生石灰の
ＣａＯの解離反応を進行する触媒の如き作用も示す。Therefore, the remarkable increase in desulfurization reaction efficiency is thought to be due to the synergistic effect of fluorite, soda ash, cryolite, and fluorite. Fluorite, fluorite soda, soda ash, and cryolite float to the top of hot metal in an unreacted state. It is effective against. Fluorite lowers the melting point of the surface layer of quicklime, creating surface strength! It becomes active and promotes reactions with sodium fluoride, soda ash, and cryolite. Here, soda fluoride, soda ash,
Cryolite not only acts as a fluxing agent, but also acts as a catalyst to advance the dissociation reaction of CaO in quicklime.

しかも、弗化ソーダ、ソーダ灰、氷晶石自身も分解して
Ｎａを生成するために、ＮａＫよる脱硫反応が進行する
。Furthermore, since the sodium fluoride, soda ash, and cryolite themselves are also decomposed to generate Na, the desulfurization reaction by NaK progresses.

本発明の脱硫剤は総重量１００重量部中カルシウムカー
バイド２０−６５重量部を含むが、前記カルシウムカー
バイドは市販カルシウムカーバイド塊を微粉砕してなる
カルシウムカ−バイト徽粉で、その粒度範囲は粒径７４
＃以下が７０重量％以上とする必要がある。上記の如く
力ルシウムカーバイドの粒度範囲を限定する理由は粒径
７４μ以下が７０重量％未満であるとカルシウムカーバ
イドの脱硫反応効率が低下するからである。The desulfurization agent of the present invention contains 20-65 parts by weight of calcium carbide in 100 parts by weight of the total weight, and the calcium carbide is calcium carbide powder obtained by finely pulverizing commercially available calcium carbide lumps, and the particle size range is granular. Diameter 74
It is necessary that # or less be 70% by weight or more. The reason why the particle size range of lucium carbide is limited as described above is that if the particle size of 74 μm or less is less than 70% by weight, the desulfurization reaction efficiency of calcium carbide decreases.

また、カルシウムカーバイドの配合割合を限定する理由
はその配合量が総重量１００重量部中２０重量部未満で
は脱硫率が下が９、脱硫剤の使用量が増加するからであ
り、一方配合量が６５重量部を越えても脱硫率をさらに
上昇させることができないばかりでなく、脱硫剤の使用
量も低減させることができず脱硫剤コストが上昇する。The reason for limiting the blending ratio of calcium carbide is that if the blending amount is less than 20 parts by weight out of 100 parts by weight, the desulfurization rate will decrease and the amount of desulfurizing agent used will increase. Even if it exceeds 65 parts by weight, not only the desulfurization rate cannot be further increased, but also the amount of desulfurization agent used cannot be reduced, resulting in an increase in desulfurization agent cost.

生石灰は市販の生石灰塊を粉砕、整粒してなる生石灰粉
粒であり、その粒度範囲としては粒径０．２〜ｌａｗの
ものを４０重量−以上とする必要がある。生石灰粉粒の
粒度範囲を限定する理由は生石灰微粉は付着凝集力が著
しく大きいため、粒径０．２〜ｌ＋ｗのものが４０重量
％未満であって粒径０．２Ｈ以下のものが多くなると吹
込装置の配管内で閉塞が起り溶銑中へ脱硫剤を吹き込む
ことができなくなるからであり、また粒径が１ｆｉを超
えるものが多くなると脱硫ｙ応速度が急激に低下するか
らである。Quicklime is quicklime powder obtained by crushing and sizing commercially available quicklime lumps, and the particle size range of the quicklime is 0.2~law and it is necessary to have a particle size of 40 weight or more. The reason for limiting the particle size range of quicklime powder particles is that quicklime powder has a significantly large adhesion and cohesive force. This is because a blockage occurs in the piping of the blowing device, making it impossible to blow the desulfurizing agent into the hot metal.Also, if the number of particles exceeding 1 fi increases, the desulfurization response rate will drop sharply.

生石灰の配合割合は総重量１００重量部中７５〜８０重
量部とする必要がある。生石灰の配合割合を限定する理
由は配合量が８０重量部未満では生石灰が脱硫にあまり
寄与しないために脱硫剤の使用量が実質的に増大するか
らであり、配合量が７５重量部を越えるとカルシウムカ
ーバイドの含有量が減少して脱硫率が下がるからである
。The blending ratio of quicklime needs to be 75 to 80 parts by weight out of 100 parts by weight of the total weight. The reason for limiting the blending ratio of quicklime is that if the blending amount is less than 80 parts by weight, the quicklime will not contribute much to desulfurization and the amount of desulfurizing agent used will increase substantially; if the blending amount exceeds 75 parts by weight, This is because the content of calcium carbide decreases and the desulfurization rate decreases.

螢石の配合割合は総重量１００重量部中１−１０重量部
とする必要がある。螢石の配合量が総重量１００重量部
中１重量部未満では脱硫反応効率を向上させることがで
きず、一方配合量が１０重量部を越えても脱硫反応効率
をさらに向上させることができず、むしろ浸漬ランス等
の耐火物の損耗が激しくなる。The blending ratio of fluorite needs to be 1-10 parts by weight per 100 parts by weight of the total weight. If the blending amount of fluorite is less than 1 part by weight out of 100 parts by weight, the desulfurization reaction efficiency cannot be improved, and on the other hand, if the blending amount exceeds 10 parts by weight, the desulfurization reaction efficiency cannot be further improved. In fact, the wear and tear on refractories such as immersion lances becomes more severe.

螢石の粒度範囲は通常の吹込装置で搬送ガスにより搬送
できる粒度範囲であれば良く、好ましくはその大部分が
１ｆｉ以下の粒径とする。The particle size range of the fluorite may be within the particle size range that can be transported by a carrier gas using a normal blowing device, and preferably most of the particles have a particle size of 1 fi or less.

弗化ソーダ、ソーダ灰、氷晶石の何れか１種または２種
以上の配合割合は総重量１００重量部中０．５〜５重量
部とする必要がある。弗化ソーダ、ソーダ灰、氷晶石の
何れか１種または２種以上の配合量は総重量１００重量
部中０．５重量部未満では螢石との前述したような相乗
作用が有効に発揮されないために脱硫反応効率が向上し
ないからであり、配合量が５重量部を越えても脱硫反応
効率をさらに向上させることができず、むしろ発煙、発
炎現象が激しくな９、かつ浸漬ランス等の耐火物の損耗
が激しくなる。The blending ratio of one or more of sodium fluoride, soda ash, and cryolite must be 0.5 to 5 parts by weight based on 100 parts by weight of the total weight. If the amount of any one or more of sodium fluoride, soda ash, and cryolite is less than 0.5 parts by weight based on 100 parts by weight of the total weight, the synergistic effect with fluorite as described above will be effectively exhibited. This is because the desulfurization reaction efficiency does not improve even if the amount exceeds 5 parts by weight. The wear and tear of refractories becomes severe.

弗化ソーダ、ソーダ灰、氷晶石の粒度範囲は通常の吹込
装置で搬送ガス圧より搬送できる粒度範囲であれば良く
、好ましくはその大部分が１厘以下の粒径とする。The particle size range of the soda fluoride, soda ash, and cryolite may be within the particle size range that can be conveyed by the carrier gas pressure using a normal blowing device, and preferably most of them have a particle size of 1 liter or less.

本発明の脱硫剤には脱硫反応効率をさらに向上　−させ
るためにアルミナを配合すること有利である。It is advantageous to add alumina to the desulfurization agent of the present invention in order to further improve the desulfurization reaction efficiency.

アルミナとしては市販のアルミナで十分でありＡｌ２Ｏ
５含有量８０％以上のものが好ましく、後述するアルミ
残灰を酸化処理して含有されている金属ＭｔＡ＃Ｏｓに
して用いることもできる。Commercially available alumina is sufficient as the alumina, and Al2O
5 content of 80% or more is preferable, and the metal MtA#Os can be used by oxidizing residual aluminum ash, which will be described later.

アルミナを配合すると溶銑上へ浮上したカルシウムカー
バイドが溶銑上の雰囲気により酸化され生成した生石灰
および脱硫剤自身に配合されている生石灰の表層部がア
ルミナによってＣａＯ−ｋｌｚｏｓ系化合物となり前述
した螢石と弗化ソーダ、ソーダ灰、氷晶石の何れか１種
または２種以上との相乗作用が促進され脱硫反応効率が
さらに向上する。When alumina is blended, the calcium carbide that floats to the top of the hot metal is oxidized by the atmosphere above the hot metal, and the surface layer of the quicklime and the quicklime that is blended in the desulfurization agent itself becomes a CaO-klzos-based compound due to the alumina, and the above-mentioned fluorite and fluorite are mixed together. The synergistic effect with any one or more of sodium chloride, soda ash, and cryolite is promoted, and the desulfurization reaction efficiency is further improved.

すなわち、脱硫反応層がＣａＯ−ｋ１２０ｓ系化合物色
々ることによりＣａＯのみに比べて流動性が増し脱硫反
応層におけるＣａＳの離脱を促進し新しいＣａＯ表面が
生成されるためと考えられる。That is, it is thought that this is because the desulfurization reaction layer contains various CaO-k120s compounds, which increases fluidity compared to CaO alone, promotes the separation of CaS in the desulfurization reaction layer, and generates a new CaO surface.

アルミナの配合割合は総重量１００重量部中５〜１５重
量部であることが好適である。その配合量が総重１００
重量部中５重量部未満では螢石と弗化ソーダ、ソーダ灰
、氷晶石の何れか１種または２種以上との相乗作用が促
進されな論ために脱硫反応効率が向上しないからであり
、配合量が１５重置部を越えるとカルシラふカーバイド
と生石灰との含有量が少なくなり脱硫剤の使用量が増大
して脱硫剤コストを実質的に減少することができないか
らである。The blending ratio of alumina is preferably 5 to 15 parts by weight based on 100 parts by weight of the total weight. The total amount is 100
If it is less than 5 parts by weight, the desulfurization reaction efficiency will not be improved because the synergistic action between fluorite and any one or more of sodium fluoride, soda ash, and cryolite will not be promoted. This is because if the blending amount exceeds 15 parts, the content of calsilaf carbide and quicklime decreases, and the amount of desulfurizing agent used increases, making it impossible to substantially reduce the cost of the desulfurizing agent.

アルミナの粒度範囲は通常の吹込装置で搬送ガスにより
搬送できる粒度範囲であれば良く、その大部分が１ｍ以
下の粒径であることが好ましい。The particle size range of the alumina may be within the particle size range that can be transported by a carrier gas using a normal blowing device, and it is preferable that the majority of the particles have a particle size of 1 m or less.

本発明の脱硫剤にあっては、その脱硫反応速度をさらに
上昇させるためにアルミ残灰、あるいは上記アルミナと
共にアルミ残灰を配合することができる。In the desulfurization agent of the present invention, in order to further increase the desulfurization reaction rate, aluminum residual ash or aluminum residual ash can be blended with the alumina described above.

本発明で用いられるアルミ残灰は、アルミニウム産業廃
棄物であって、金属ＡＩ含有量が１０％重量以上のもの
が好ましい、その分析例を第１表に示す。The aluminum residual ash used in the present invention is aluminum industrial waste and preferably has a metal AI content of 10% or more by weight. Table 1 shows an analysis example thereof.

第１表 アルミ残灰は金属ＡＩ、ＡｌｚＱ３を主成分とし、その
他８ｉ０ｚ、　Ｆｅ２ｅｓ、Ｃａｂ、　ＭｇＱ、ｆ−ｃ
、　Ｎａ、　Ｆ、　Ｎ等を含有する。Table 1 Aluminum residual ash mainly consists of metal AI, AlzQ3, and others 8i0z, Fe2es, Cab, MgQ, f-c
, Na, F, N, etc.

特開昭５６−５８９１２号公報に見られる如く、脱硫反
応効率の向上と処理コストの低減をはかるたメニ、カル
シウムカーバイドと生石灰とｙｖミａ灰とを主成分とし
て含有してなる脱硫剤が提案されている。しかしながら
前記提案は脱硫剤の脱硫反応効率の向上および脱硫剤コ
ストの低減に対してはある程度効果を奏しているが、本
発明者等は螢石と弗化ソーダ、ソーダ灰、氷晶石の何れ
か１種または２種以上と共にアルミナおよびまたはアル
ミ残灰とを配合すると脱硫反応速度が著しく上昇するこ
とを新規に知見した。As seen in JP-A No. 56-58912, a desulfurization agent containing calcium carbide, quicklime, and YV mia ash as main components was proposed to improve desulfurization reaction efficiency and reduce processing costs. has been done. However, although the above proposal has been effective to some extent in improving the desulfurization reaction efficiency of the desulfurization agent and reducing the cost of the desulfurization agent, the present inventors have not yet determined whether fluorite, sodium fluoride, soda ash, or cryolite. It has been newly discovered that the rate of desulfurization reaction increases significantly when alumina and/or aluminum residual ash is blended with one or more of the following.

アルミ残灰は含有する金属Ｍが溶銑中の脱酸作用を有す
ると共Ｋ、含有するＡｌｔｏｓが前述のアルミナと同様
の螢石と弗化ソーダ、ソーダ灰、氷晶石の何れか１種ま
たは２種以上との相乗作用を促進する。Aluminum residue ash contains metal M that has a deoxidizing effect in hot metal, and Altos that it contains is any one of fluorite, soda fluoride, soda ash, cryolite, etc. similar to the above-mentioned alumina, or Promote synergy with two or more species.

アルミ残灰の配合割合は総重量１００重量部中２〜１５
重量部であることが好適である。その配合量が総重量１
００重量部中２重量部未満では溶銑中の脱酸作用がなく
なり、弗化ソーダ、ソーダ灰、氷晶石の何れか１種また
は２種以上との相乗作用が促進されないために脱硫反応
速度が上昇しないからであり、配合量が１６重量部を越
えるとカルシウムカーバイドと生石灰との含有量が少な
くなり脱硫剤の使用量が増大して脱硫剤コストを実質的
に減少することができないからである。The mixing ratio of aluminum residual ash is 2 to 15 parts per 100 parts by weight of the total weight.
Parts by weight are preferred. The total amount is 1
If it is less than 2 parts by weight in 0.00 parts by weight, the deoxidizing effect in the hot metal will be lost, and the synergistic effect with any one or more of sodium fluoride, soda ash, and cryolite will not be promoted, so the desulfurization reaction rate will be reduced. This is because if the blending amount exceeds 16 parts by weight, the content of calcium carbide and quicklime will decrease, and the amount of desulfurization agent used will increase, making it impossible to substantially reduce the desulfurization agent cost. .

アルミ残灰の粒度範囲は通常の吹込装置で搬送ガスによ
り搬送できる粒度範囲であれば良く、その大部分がＩｓ
ｍ以下の粒径であることが好ましい。The particle size range of aluminum residual ash may be within the particle size range that can be transported by a carrier gas using a normal blowing device, and most of it is Is.
It is preferable that the particle size is less than m.

本発明の脱硫剤に脱硫剤の分散を向上させるためにカル
シウムカーバイド製造用密閉式電気炉に付設された乾式
集塵装置により集塵されるダスト（以下、単に乾式ダス
トという）を総重量１（１０重量部中ｌθ〜２５重量部
含有させることができる。In order to improve the dispersion of the desulfurizing agent into the desulfurizing agent of the present invention, the dust collected by the dry dust collector attached to the closed electric furnace for producing calcium carbide (hereinafter simply referred to as dry dust) is collected by a total weight of 1 ( It can be contained in an amount of lθ to 25 parts by weight in 10 parts by weight.

また、前述の乾式ダスト以外に必要に応じて、炭酸カル
シウム、石灰窒素からジシアンジアミドを製造する際の
残渣であるジアミド石灰などの溶銑温度下で二酸化要素
を発生する物質、消石灰、灰硼鉱などの溶銑温度下で水
を発生する物質、ポリエチレンなどの溶銑温度下で水素
を発生する物質、コークス、黒鉛、無煙炭などの灰素物
質、ステアリン酸、ステアリン酸塩などの固体潤滑剤な
どを配合することができる。In addition to the above-mentioned dry process dust, if necessary, substances that generate carbon dioxide elements at hot metal temperatures such as calcium carbonate and diamide lime, which is a residue from the production of dicyandiamide from lime nitrogen, slaked lime, and perioborite, etc. Mixing substances such as substances that generate water at hot metal temperature, substances that generate hydrogen at hot metal temperature such as polyethylene, ash substances such as coke, graphite, and anthracite, and solid lubricants such as stearic acid and stearate salts. I can do it.

次に、本発明を実施例について比較例と併わせで具体的
に説明する。Next, the present invention will be specifically described in terms of examples and comparative examples.

実施例１ならびく比較例１ 脱硫剤に用いたカルシウムカーバイドはカルシウムカー
バイド塊を微粉砕してエアーセパレーターにて粒径０．
１鱈以上の粒子を除去し、粒径７４μ以下が８１，７０
１８４重量％になるように調整してなるＣａＣ２含有量
７８重量％のカルシウムカーバイド粉末であった。Comparative Example 1 Similar to Example 1 Calcium carbide used as a desulfurizing agent was obtained by finely pulverizing calcium carbide lumps and using an air separator to obtain a particle size of 0.
Particles larger than 1 cod are removed, and particles with a diameter of 74μ or less are 81,70
The calcium carbide powder had a CaC2 content of 78% by weight and was adjusted to 184% by weight.

生石灰は生石灰塊を微粉砕してエアーセパレーターにて
粒径０．１ｆｉ以上の粒子を除去して、粒径６５μ以下
が８５重量％になるように調整してなる生石灰粉末およ
び生石灰塊を粉砕して目の開き０．２藺と１鱈のフルイ
で粒径０．２　Ｗ下Ｏ重量％かつ１１ヒフ０重量％、粒
径０．２　ｊ下６０重量％かつ１ｍ上１ＯＮ量％、粒径
０．２ｍ１Ｆ４５重量−かつ１部上５重量％になるよう
に分級しそれぞれ粒径０．２〜１ｍが８０．４０，５０
重量％に調整してなる生石灰粉粒であり、ＣａＯ含有量
は何れも９６重量−であった。Quicklime is made by finely pulverizing quicklime lumps, removing particles with a particle size of 0.1fi or more using an air separator, and adjusting the amount of particles with a particle size of 65μ or less to 85% by weight.The quicklime powder and quicklime lumps are then ground. Using a sieve with a mesh size of 0.2 and 1 cod, the particle size is 0.2% by weight of O below and 0% by weight of 11%, particle size is 0.2% by weight below 60% by weight of below J and 1% by weight of above 1m, particle size 0.2m1F45 weight - and classified so that 1 part and 5% by weight respectively, particle size 0.2 ~ 1m is 80.40, 50
These were quicklime powder particles adjusted to % by weight, and the CaO content was 96% by weight.

蛍石は市販の蛍石粉粒で、そのＣａＦ２含有量は８０重
量％、その粒度は粒径０．１ｍ以下が８１重量％であっ
た。The fluorite was commercially available fluorite powder, and its CaF2 content was 80% by weight, and its particle size was 81% by weight with a particle size of 0.1 m or less.

弗化ソーダはＮａＦ含有量が９７重量％、その粒度は粒
径７４ｊ＋以下９１重量％、ソーダ灰はＮ＆２■コ含有
量が９８重量％、その粒度は０．５　ｍ以下８９重量％
、氷晶石はＮａ５ＡＪＦｓ含有量が９７重量％、その粒
度は粒径７り以下７６重量％の粉粒であった。Soda fluoride has a NaF content of 97% by weight, and its particle size is 74j+ or less, which is 91% by weight.Soda ash has a N&2■ content of 98% by weight, and its particle size is 89% by weight, which is 0.5 m or less.
The cryolite had a Na5AJFs content of 97% by weight, and its particle size was 76% by weight with a particle size of 7 mm or less.

アルミナはバイヤーアルミナであってＡ１２ｏｓ含有量
が９８重量％、その粒度は粒径１４７＃以下８５重量％
の粉末であった。The alumina is Bayer alumina, and the A12os content is 98% by weight, and its particle size is 85% by weight with a particle size of 147# or less.
powder.

アルミ残灰は１組成が前に挙げた第１表のようであって
、その粒度はＯ−６ｍ以下９１重量％の粉粒であった。The composition of the aluminum residual ash was as shown in Table 1 above, and the particle size was 91% by weight of particles with a particle size of 0-6m or less.

脱硫剤は各種配合物を窒素気流中で流動化混合して調製
した。第２表に各種脱硫剤の配合比率を示す。Desulfurization agents were prepared by fluidizing and mixing various formulations in a nitrogen stream. Table 2 shows the blending ratios of various desulfurizing agents.

尚、必要に応じて第２表に示す脱硫剤にさらに粒度が粒
径７４μ以下８４重量襲の炭酸力／Ｉ／Ｓ／ウム粉末ま
九は乾式ダストを配合して溶銑中へ吹き込んだ。Incidentally, if necessary, dry dust of carbonic acid/I/S/Um powder having a particle size of 74 μm or less and 84% by weight was added to the desulfurization agent shown in Table 2 and blown into the hot metal.

第２表において、それぞれの成分の配合比率はポ量百分
率で示し、その合計は１００重量幅である。In Table 2, the blending ratio of each component is shown in percentage, and the total is 100% by weight.

前述の如くして調製した脱硫剤約２４０＃を取鍋に採っ
た硫黄濃度的０．０４　％の溶銑約８０ｔに内径２．５
１の耐火製フンスバイグを約１．５１１浸漬し、窒素ガ
ス１．ＯＮｗｌ／ｍと共に約２０幻／ｍの速度で約１２
分間吹き込んだ、その結果を第８表に示す。The desulfurization agent prepared as described above was placed in a ladle of approximately 80 tons of hot metal with a sulfur concentration of 0.04% and an inner diameter of 2.5 mm.
A refractory Hunsweig of 1 was immersed for about 1.51 hours, and 1. About 12 at a speed of about 20 phantom/m with ONwl/m
The results are shown in Table 8.

第８表において、脱硫剤の組成は第２表に示し念配合Ａ
−Ｐ１００重量部に対する乾式ダスト、戻酸力〜シウム
の配合量を重量部で示したものである。脱硫剤原単位、
脱硫率、ＣａＣｚ脱硫反応効率はそれぞれ溶銑中の硫黄
濃度を処理前８１（％〕、処理後８ｚ（％）、脱硫処理
した溶銑量をＰ（ｔ）、溶銑に吹き込んだ脱硫剤の量を
Ｑ　（＃入脱硫剤中のＣａＣｚ含有量をＲ（％〕で表わ
す時、Ｑ／Ｐ（ｈｙｔ−Ｐｉｇ）、１０１００（８１−
８／Ｓｓ（％〕、２Ｘ１０’、Ｐ（８１−８ｚ）／Ｑ−
Ｒ（％〕で求めた値である。また、配管閉塞の状況はそ
れぞれの吹込脱硫の操業で配管閉塞が全く起らなかった
もの○印、非常圧よく起ったものをＸ印で表わした。In Table 8, the composition of the desulfurizing agent is shown in Table 2.
- Dry dust and return acid power to 100 parts by weight of P - the blended amount of sium is shown in parts by weight. Desulfurization agent basic unit,
The desulfurization rate and CaCz desulfurization reaction efficiency are determined by the sulfur concentration in the hot metal being 81 (%) before treatment, 8z (%) after treatment, the amount of desulfurized hot metal P (t), and the amount of desulfurization agent blown into the hot metal Q (# When the CaCz content in the desulfurizing agent is expressed as R (%), Q/P (hyt-Pig), 10100 (81-
8/Ss(%), 2X10', P(81-8z)/Q-
This is the value calculated in R (%).In addition, the situation of pipe blockage is indicated by ○ if no pipe blockage occurred during each blow desulfurization operation, and by X if it occurred frequently under extreme pressure. .

第８表において、脱硫４１Ｎ１Ｇは本発明の実施例であ
りＣａＣｚ説硫反応効率が４２．５％以上の値を示して
おり、比較例である脱硫Ａ１１〜１６に比べて良好な結
果を示している。In Table 8, Desulfurization 41N1G is an example of the present invention and exhibits a CaCz sulfur reaction efficiency of 42.5% or more, showing better results than Desulfurization A11 to 16, which are comparative examples. There is.

脱硫ム１１はカルシウムカーバイドと次酸カルシウムと
から成る脱硫剤を吹き込んだ場合のものであるが、力Ａ
／Ｖウムカーバイドが溶銑表面上へ浮上後酸化され生成
した生石灰が脱硫に寄与しないためＣａＣ２説硫反応効
率は２７．８％と低いものであった。The desulfurization film 11 is the one in which a desulfurization agent consisting of calcium carbide and calcium suboxide is injected.
The CaC2 theory sulfur reaction efficiency was as low as 27.8% because the quicklime produced by oxidation of /Vum carbide after it floated onto the surface of the hot metal did not contribute to desulfurization.

脱硫Ａ１２は脱硫剤に蛍石に加えて弗化ソーダ、ソーダ
灰、氷晶石が配合されていないためＣａＣｚ脱硫反応効
率が８２．６％と低くなっている。Desulfurization A12 does not contain sodium fluoride, soda ash, and cryolite in addition to fluorite as a desulfurization agent, so the CaCz desulfurization reaction efficiency is as low as 82.6%.

脱硫扁１８は生石灰が微細なため配管閉塞が非常によく
起９脱硫できなかった。Desulfurization flat 18 was unable to desulfurize because the quicklime was so fine that the pipes were often clogged.

脱硫Ａ１４は本発明の実施例に比べて力ＩＶＶウムカー
バイドの粒度が粗く、脱硫Ａ１６は生石灰の粒度が粗い
ためＣａＣｚ脱硫反応効率はそれぞれ８８．４％。In desulfurization A14, the particle size of IVV carbide is coarser than in the examples of the present invention, and in desulfurization A16, the particle size of quicklime is coarser, so the CaCz desulfurization reaction efficiency is 88.4%.

８１．４％と低くなっている。The rate is low at 81.4%.

さらに、本発明の実施例においてアルミナ、アルミ残灰
を配合しなかっ九脱硫剤を使用した脱硫應２．８ノＣａ
Ｃｚ脱硫度応効率は４６６７％、４４．０憾であるのに
対し、アルミナを配合した脱硫剤を使用した脱硫憲４〜
６のＣ１１Ｃ２脱硫反応効率は４９．６〜５０．４％で
あって向上しており、さらＫまたアルミナとアルミ残灰
とを配合した脱硫剤を使用した脱硫Ａ７のＣａＣｚ脱硫
反応効率は６０．９％であり、アルミ残灰を配合した脱
硫剤を使用した脱硫Ａ８．９のＣａＣ冨説硫反応効率は
６１．１％、−５８，４％と著しく向上している。また
、脱硫Ａ７〜９のＣａＣを脱硫反応効率はアルミ残灰に
加えて蛍石、弗化ソーダ、ソーダ灰、氷晶石を配合しな
かった脱硫剤を使用した脱硫＆１５のそれに比べても著
しく向上しており、力〃シウムカーバイドを生石灰で希
釈しなかった脱硫剤を使用した脱硫墓１１と比べるとカ
ルシウムカーバイドの配合比率が低いＫもかかわらず原
単位を増やすことなく等しい脱硫率が得られることがわ
かる。Furthermore, in an example of the present invention, a desulfurization solution containing no alumina or aluminum ash and using a desulfurization agent of 2.8
The Cz desulfurization degree response rate is 4667%, 44.0%, whereas the desulfurization rate using desulfurization agent containing alumina is 4~
The C11C2 desulfurization reaction efficiency of A7 was 49.6 to 50.4%, which is an improvement, and the CaCz desulfurization reaction efficiency of desulfurization A7 using a desulfurization agent containing alumina and aluminum residual ash was 60. 9%, and the CaC-rich sulfur reaction efficiency of desulfurization A8.9 using a desulfurization agent containing aluminum residual ash was significantly improved to 61.1% and -58.4%. In addition, the desulfurization reaction efficiency of CaC in desulfurization A7 to A9 is significantly higher than that in desulfurization &15, which uses a desulfurization agent that does not contain fluorite, sodium fluoride, soda ash, or cryolite in addition to aluminum residual ash. Compared to Desulfurization Tomb 11, which uses a desulfurization agent that does not dilute sium carbide with quicklime, the same desulfurization rate can be obtained without increasing the basic unit despite the lower blending ratio of calcium carbide. I understand that.

以上述べてきたよう忙、本発明はカルシウムカーバイド
が生石灰で希釈されているＫもかかわらず脱硫剤の脱硫
反応効率が著しく高く、経済的に有利な脱硫剤である。As described above, the present invention is an economically advantageous desulfurizing agent that has extremely high desulfurization reaction efficiency even though calcium carbide is diluted with quicklime.

Claims (1)

【特許請求の範囲】 １、カルシウムカーバイド２０〜６５重量部と生石灰７
５〜８ＯＮ量部と螢石１〜１０重量部と弗化ソーダ、ソ
ーダ灰、氷晶石の何れか１１ｍ１または２種以上０．５
〜５重量部とから主として成る総重量が１００重量部で
ある溶銑の脱硫剤であって、前記カルシウムカーバイド
の７０重量−以上が’１４ｐ以下の粒径であり、前記生
石灰の４０重量外以上が０．２〜１鰭の粒径である溶銑
の吹込用脱硫剤。 ２、特許請求の範囲第１項記載の脱硫剤にアルミナ５〜
１５重量％およびまたはアルミナ残灰２〜１５重量％を
配合して成る溶銑の吹込用脱硫剤。[Claims] 1. 20 to 65 parts by weight of calcium carbide and quicklime 7
5 to 8 parts by weight of fluorite, 1 to 10 parts by weight of fluorite, and 11 ml of any of sodium fluoride, soda ash, and cryolite, or 0.5 of two or more of them.
A desulfurizing agent for hot metal having a total weight of 100 parts by weight mainly consisting of ~5 parts by weight, wherein at least 70 parts by weight of the calcium carbide has a particle size of 14p or less, and at least 40 parts by weight of the quicklime A desulfurizing agent for blowing hot metal with a particle size of 0.2 to 1 fin. 2. The desulfurizing agent described in claim 1 contains alumina 5 to
A desulfurizing agent for blowing hot metal containing 15% by weight and/or 2 to 15% by weight of alumina residual ash.
JP14014881A 1981-09-04 1981-09-04 Desulfurizer for blowing of molten iron Pending JPS5842710A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP14014881A JPS5842710A (en) 1981-09-04 1981-09-04 Desulfurizer for blowing of molten iron

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP14014881A JPS5842710A (en) 1981-09-04 1981-09-04 Desulfurizer for blowing of molten iron

Publications (1)

Publication Number Publication Date
JPS5842710A true JPS5842710A (en) 1983-03-12

Family

ID=15261982

Family Applications (1)

Application Number Title Priority Date Filing Date
JP14014881A Pending JPS5842710A (en) 1981-09-04 1981-09-04 Desulfurizer for blowing of molten iron

Country Status (1)

Country Link
JP (1) JPS5842710A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55169372U (en) * 1979-05-23 1980-12-05
JP2009108344A (en) * 2007-10-26 2009-05-21 Nippon Steel Corp Desulfurizing agent for molten metal
CN103014217A (en) * 2011-09-26 2013-04-03 攀钢集团攀枝花钢铁研究院有限公司 Desulfurizing agent and application thereof as well as molten iron krypton (KR) desulfurization method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5421914A (en) * 1977-07-21 1979-02-19 Denki Kagaku Kogyo Kk Desulfurizing agnet for molten pig iron
JPS5541912A (en) * 1978-09-14 1980-03-25 Denki Kagaku Kogyo Kk Desulfurizer for molten iron
JPS5658912A (en) * 1979-10-19 1981-05-22 Denki Kagaku Kogyo Kk Desulfurizer of molten iron

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5421914A (en) * 1977-07-21 1979-02-19 Denki Kagaku Kogyo Kk Desulfurizing agnet for molten pig iron
JPS5541912A (en) * 1978-09-14 1980-03-25 Denki Kagaku Kogyo Kk Desulfurizer for molten iron
JPS5658912A (en) * 1979-10-19 1981-05-22 Denki Kagaku Kogyo Kk Desulfurizer of molten iron

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55169372U (en) * 1979-05-23 1980-12-05
JP2009108344A (en) * 2007-10-26 2009-05-21 Nippon Steel Corp Desulfurizing agent for molten metal
CN103014217A (en) * 2011-09-26 2013-04-03 攀钢集团攀枝花钢铁研究院有限公司 Desulfurizing agent and application thereof as well as molten iron krypton (KR) desulfurization method
CN103014217B (en) * 2011-09-26 2015-07-15 攀钢集团攀枝花钢铁研究院有限公司 Desulfurizing agent and application thereof as well as molten iron krypton (KR) desulfurization method

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