JPS6169911A - Desulfurizing material for molten iron and its production - Google Patents
Desulfurizing material for molten iron and its productionInfo
- Publication number
- JPS6169911A JPS6169911A JP19598185A JP19598185A JPS6169911A JP S6169911 A JPS6169911 A JP S6169911A JP 19598185 A JP19598185 A JP 19598185A JP 19598185 A JP19598185 A JP 19598185A JP S6169911 A JPS6169911 A JP S6169911A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- desulfurization
- quicklime
- calcium carbonate
- weight
- 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
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
Abstract
Description
【発明の詳細な説明】
本発明は、石灰質粉末を酸化性雰１ＩＩＩ気で流動焙焼
して得られた、内部に炭酸カルシウムを含有する生石灰
粉からなる、融鉄の吹込み脱硫剤、および該生石灰粉の
製造法に関する。ここ′ｃ＠鉄というのは、銑鉄、鋳鉄
および鋼等の？８融物をいう。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a blown desulfurizing agent for molten iron, which is made of quicklime powder containing calcium carbonate inside, obtained by fluidized roasting of calcareous powder in an oxidizing atmosphere, and The present invention relates to a method for producing the quicklime powder. Here, 'c@iron' refers to pig iron, cast iron, steel, etc. 8. Refers to melted material.
周知のように融鉄の脱硫は、優れた性能を有する鉄ｆｆ
ＡＳ！！！品を得る為に重要な技術課題であり、脱硫剤
、及び脱硫法については数多くの提案がなされてさた。As is well known, desulfurization of molten iron is performed using iron ff, which has excellent performance.
AS! ! ! This is an important technical issue for obtaining products, and many proposals have been made regarding desulfurization agents and desulfurization methods.
脱硫剤としてはカルシウムカーバイドが最も優れた脱硫
性能を有し、カルシウムカーバイドな主成分とするもの
が広く用いられている６ しがし、その製造には多量の
電力をｚｌ“ｒｆＬ、エネルギーコストが高騰している
近ｌ←の状況下では経済的観魚からの再検討に迫られて
いる。Calcium carbide has the best desulfurization performance as a desulfurization agent, and those containing calcium carbide as the main component are widely used6. Under the current situation of soaring prices, we are being forced to reconsider economical fishing.
一万、安価な脱硫剤として知られているものの一つに生
石灰があり、該生石灰は、混焼立窯、重油焼立窯、ンヤ
フトキルン、ロークリキルノ等の装置を用い、一般に炭
酸カルシウムを主成分とする石灰石、方解石、大理石、
貝殻等を、使用目的に応じて塊状に焼皿し１次いで機械
的に粉砕し、融鉄の脱硫剤の主成分として使用されては
いるが、かぐして作られた生石灰粉目体の脱硫性能が昔
しく小さい等の問題があるので、生石灰系脱硫剤は、溶
銑脱硫における高度な脱硫性能に対する鉄鋼業界の要望
を満たすに至っていない。One of the known inexpensive desulfurizing agents is quicklime, which is produced using equipment such as co-fired standing kilns, heavy oil fired standing kilns, Nyafuto kilns, and lokuri kilns, and is generally made with calcium carbonate as its main component. limestone, calcite, marble,
Desulfurization of quicklime powder made by baking shells etc. into lumps depending on the purpose of use and then mechanically crushing them is used as the main component of desulfurization agent for molten iron. Due to problems such as poor performance, quicklime-based desulfurization agents have not yet met the steel industry's demand for high desulfurization performance in hot metal desulfurization.
また、脱硫法としては、融鉄に脱硫剤を重加し機械的に
攪拌する方法や、粉末脱硫剤をガスを用いて融鉄中に吹
込む方法等がよく知られている。Furthermore, well-known desulfurization methods include a method in which a desulfurizing agent is heavily added to molten iron and mechanically stirred, and a method in which a powdered desulfurizing agent is blown into molten iron using gas.
これ等のうち、脱硫法としては、近年、吠込み脱硫法が
特に優れた作業性と優れた脱硫効率の故に、広く採用さ
れるようになった。Among these desulfurization methods, the barring desulfurization method has been widely adopted in recent years because of its particularly excellent workability and excellent desulfurization efficiency.
この吹込み脱硫法は、脱硫剤粉末を例えば乾燥窒素等の
キャリアガスのガス流に同伴させ、融鉄中に浸漬したラ
ンスを通じて融鉄中に吹込み脱硫を行う方法である。吹
込脱硫法は、例えば高炉より受銑した混銑車を製鋼工場
に移動させる途中、脱硫ステーションで暫時停車させて
、粉末脱硫剤を混銑車中の溶銑に吹込む方法で、機械攪
拌式脱硫法（所謂オープン・レードルでのに几法等）Ｋ
代って、混銑車での吹込み脱硫が広く実用化されるに至
っている。This blowing desulfurization method is a method in which a desulfurizing agent powder is entrained in a gas flow of a carrier gas such as dry nitrogen, and desulfurization is carried out by blowing into the molten iron through a lance immersed in the molten iron. The blowing desulfurization method is a method in which, for example, a pig iron mixer car that has received pig iron from a blast furnace is temporarily stopped at a desulfurization station during transportation to a steelmaking plant, and powdered desulfurization agent is blown into the hot metal in the mixer car. (So-called open ladle method, etc.) K
Instead, blow desulfurization using a pig iron mixer has come into widespread practical use.
本明細書でいう「吹込み脱硫」とは、所謂「立性き゛」
等に対する技術用語で、具体的には、脱硫剤粉末をキャ
リアガスと共に融鉄の湯面より下部に吹込んで脱硫全行
う方法を市うものである。In this specification, "blow desulfurization" refers to so-called "stand-up desulfurization".
Specifically, it refers to a method of completely desulfurizing molten iron by blowing desulfurizing agent powder together with a carrier gas below the surface of the molten iron.
上記の吹込み脱硫法に於いては、脱硫剤粉末のキャリア
ガスに依るガス搬送性と脱硫性能とは極めて密接な関係
があり、ガス搬送性に劣る脱硫剤粉末では優れた脱硫性
能を期待することができない。In the above-mentioned blowing desulfurization method, there is an extremely close relationship between the desulfurization performance and the gas transportability of the desulfurization agent powder due to the carrier gas, and excellent desulfurization performance is expected with the desulfurization agent powder, which has poor gas transportability. I can't.
前記したよう匡、脱硫性能の十分発揮されていない、生
石灰の脱硫性能の向上に関しては、原料石灰石粉を非散
化性雰囲気で堰焼し、生成ＣａＯ−次結晶の表面に無定
形炭素を析出させた実質的に生石灰と炭素からなる脱硫
剤を用いる特開昭５４−５０４１４号等の提案、ガス搬
送性を改善したシリコン系界面活性剤添加の生石灰粉を
用いる特開１１’３５５−１１０７１２号の提案、内部
にｃａｃｏ。As mentioned above, in order to improve the desulfurization performance of quicklime, whose desulfurization performance is not fully demonstrated, raw limestone powder is weir-calcined in a non-dispersing atmosphere, and amorphous carbon is precipitated on the surface of the generated CaO-crystals. Japanese Patent Application Laid-Open No. 11'355-110712 uses quicklime powder added with a silicone surfactant that improves gas transportability. Suggestion, caco inside.
を存在させた生石灰粒を用いる特開［５２−１１１８１
３号の提案、粉状の生石灰に粉状の炭酸カルシウムを添
加混合した％開昭５５−７３８０９号の提案、等がある
。JP-A No. 52-11181 using quicklime particles containing
There is a proposal No. 3, and a proposal No. 73809/1989 in which powdered quicklime is mixed with powdered calcium carbonate.
しかしながら、これら生石灰系脱硫剤は、特開昭５５−
１１０７１２号提案のものを除いて、吹込み脱硫の際、
キャリアガス流によるガス搬送性が必ずしも良好でなく
、脱硫性能も不十分であることが判った。However, these quicklime-based desulfurization agents are
Except for the one proposed in No. 110712, during blow desulfurization,
It was found that the gas transportability by the carrier gas flow was not necessarily good and the desulfurization performance was also insufficient.
本発明者は、吹込み脱硫法において生石灰の有する脱硫
性能を十分に発揮させるだめ鋭意研究を重ねた結果、石
灰質粉末を酸化性雰囲気下で流動焙焼した生石灰粉が、
微粉末で極めてガス搬送性に優れるものであり、更に、
該生石灰粉の内部に、炭酸カルシウムを１５重量％超え
６０ｉ量チ以下含有したものが、吹込み脱硫法において
極めて優れた脱硫性能を発揮するという意外な発見をし
た。The inventor of the present invention has conducted intensive research to fully demonstrate the desulfurization performance of quicklime in the blow desulfurization method, and has discovered that quicklime powder obtained by fluidized calcareous roasting of calcareous powder in an oxidizing atmosphere is
It is a fine powder with extremely excellent gas transport properties, and furthermore,
We have made the surprising discovery that the quicklime powder containing more than 15% by weight of calcium carbonate and less than 60% of calcium carbonate exhibits extremely excellent desulfurization performance in the blow desulfurization method.
本願明細書で、「石灰質粉末」とは、炭酸カルシウム主
成分とする、粒径１００μ以下の粉末が９０重ｉ％以上
、好ましくは粒径６０μ以下の粉末が８０３ｉ％以上の
石灰質物質の粉末をいう。In the present specification, "calcareous powder" refers to powder of a calcareous substance containing calcium carbonate as a main component and containing at least 90% by weight of powder with a particle size of 100μ or less, preferably 803i% or more of powder with a particle size of 60μ or less. say.
これらのものとして、石灰石、方解石、大理石、貝殻、
等の粉末や、化学反応で生底した微細な炭酸カルシウム
を主成分とするもの、或はジアミド石灰等を挙げること
ができるが、ジアミド石灰はそれ自体で微細な粉末でち
り、該粉末を酸化性雰囲気下でゐ動焙焼し得られる生石
灰粉は、特に優れたガス搬送性並びに脱硫性能を示すの
で好適に用い得るものである。These include limestone, calcite, marble, shells,
, etc., those whose main component is fine calcium carbonate produced by a chemical reaction, or diamide lime, etc. However, diamide lime itself is a fine powder, and the powder is oxidized. Quicklime powder obtained by dynamic roasting in a neutral atmosphere exhibits particularly excellent gas transportability and desulfurization performance, and can therefore be suitably used.
本Ｂ明細書で、「ジアミド石灰」とは、水溶液ないし水
懸濁液から、化学反応によって沈降した微細な沈降性炭
酸カルシウムと炭素の混合物の意味で用いるもので６る
。In this specification, "diamide lime" is used to mean a mixture of fine precipitated calcium carbonate and carbon that is precipitated from an aqueous solution or suspension by a chemical reaction.
ジアミド石灰としては、例えば、石灰窒素よシジシアン
ジアミド製造の際や、石灰窒素よりチオ尿素等を製造す
る際、等に副生する炭酸カルシウムと炭素の混合物等が
あり、好ましくは石灰窒素よシジシアンジアミドを製造
する際に得られる、炭酸カルシウムと炭素の混合物が最
適に用いられる。ジシアンジアミドの製造は、石灰窒素
水懸濁液に炭酸ガスを反応させることにより行なわれ、
その際の濾過残渣である副生ジアミド石灰は、一般に、
炭酸カルシウム７０〜９０％、炭素５〜１５チ、その他
に酸化鉄、酸化アルミニウム、酸化珪素等の不純物を含
有しておシ、極めて微細な炭酸カルシウムと炭素を主成
分とする混合物である。Diamide lime includes, for example, a mixture of calcium carbonate and carbon that is produced as a by-product when producing sydicyandiamide from lime nitrogen, or when producing thiourea etc. from lime nitrogen, and is preferably a mixture of calcium carbonate and carbon, which is produced when producing thiourea etc. from lime nitrogen. A mixture of calcium carbonate and carbon, obtained in the production of carbon, is optimally used. Dicyandiamide is produced by reacting a lime nitrogen aqueous suspension with carbon dioxide.
The by-product diamide lime, which is the filtration residue at that time, is generally
It is a mixture containing 70-90% calcium carbonate, 5-15% carbon, and other impurities such as iron oxide, aluminum oxide, and silicon oxide, and whose main components are extremely fine calcium carbonate and carbon.
本発明で用いる前記せる石灰質粉末の焙焼法としては、
酸化性雰囲気下で流動焙焼するものであるが、本願明細
書で「酸化性雰囲気下で流動焙焼コするとは、焙焼熱源
、例えば−酸化炭素、天然ガス、プロパン等の気体燃料
、重油等の液体燃料及びコークス粉等の固体燃料（ジア
ミド石灰の場合は、該石灰の外殻部に存在する炭素も燃
料となる）が、完全燃焼するのに必要な理論酸素量よシ
も過剰の酸素が存在する条件で、焙焼することを謂う意
味で用いるものである。好ましくは焙焼熱源の完全燃焼
に必要な理論酸素量の１．０５倍以上、更に好ましくは
１．１〜２−５倍、最も好ましくは１．１〜２．２倍の
酸素が焙焼炉に供給される。酸素量が１〜０５倍未満と
少な過ぎては、石灰質粉末の外部を短時間に急激に加熱
して、生石灰に転化することが困ｍｒｔｃなるので好ま
しくない。The method of roasting the calcareous powder used in the present invention is as follows:
Fluidized roasting is carried out in an oxidizing atmosphere, but in the specification of this application, "fluidized roasting in an oxidizing atmosphere" refers to a roasting heat source such as carbon oxide, natural gas, gaseous fuel such as propane, heavy oil, etc. Liquid fuels such as and solid fuels such as coke powder (in the case of diamide lime, the carbon present in the outer shell of the lime is also used as fuel) are in excess of the theoretical amount of oxygen required for complete combustion. It is used to refer to roasting in the presence of oxygen. Preferably 1.05 times or more the theoretical amount of oxygen required for complete combustion of the roasting heat source, more preferably 1.1 to 2 - 5 times more oxygen, most preferably 1.1 to 2.2 times more oxygen is supplied to the roasting furnace.If the amount of oxygen is too low, less than 1 to 05 times, the outside of the calcareous powder will be heated rapidly in a short time. This is not preferable because it makes it difficult to convert into quicklime.
而して、石灰質粉末を酸化性雰囲気で流動焙焼して得ら
れる本発明の生石灰粉の内部には、炭酸カルシウムが１
５重量％を超え６０重量％以下の愈で残存する必要があ
る。Therefore, the quicklime powder of the present invention obtained by fluidized calcining of calcareous powder in an oxidizing atmosphere contains 1 calcium carbonate.
It is necessary to remain with a content of more than 5% by weight and less than 60% by weight.
生石灰粉中の炭酸カルシウムの含有量が１５重量％以下
のものでは、吹込み脱硫において脱硫性能が低下するの
で好ましくなく、また、６０’ｉｉチを超えると、脱硫
反応にあづかる生石灰の量が減少し、同様に脱硫性能が
低下するので好ましくなく、脱硫性能から微細な生石灰
粉中の炭酸カルシウムの含有量が、好ましくは１５重量
％を超え４５重量％以下、更に好ましくは２５重量％を
超え４５重量％以下、最も好ましくは３０重量％を超え
４５重量％以下の生石灰粉のものがよい。If the content of calcium carbonate in the quicklime powder is less than 15% by weight, the desulfurization performance in blow desulfurization will deteriorate, which is undesirable.If it exceeds 60%, the amount of quicklime that participates in the desulfurization reaction will decrease. This is undesirable because the desulfurization performance also decreases, and from the viewpoint of desulfurization performance, the content of calcium carbonate in the fine quicklime powder is preferably more than 15% by weight and less than 45% by weight, more preferably more than 25% by weight. Quicklime powder containing 45% by weight or less, most preferably more than 30% by weight and less than 45% by weight is preferred.
本発明者等が、石灰質粉末、特にジアミド石灰ｔ−酸化
性雰囲気で種々の条件で流動焙焼した、内部に炭酸カル
シウムを含有する生石灰粉の形態について、電子顕微鏡
で広範囲に及ぶ研究を行った結果、意外にも、模型的に
矛２図に示すように、内部の炭酸カルシウムの量が１５
重量％以下のものでは、生石灰外殻部から内部に達する
ガス抜は穴、即ち、炭酸カルシウムの熱分解によって生
圧した炭酸ガスの抜は穴が大きく、１５重量％を超えた
ものでは小さいことを発見した。The present inventors have carried out extensive studies using electron microscopy on the morphology of calcareous powders, particularly diamide lime t-quicklime powders containing internal calcium carbonate, fluidized and roasted under various conditions in an oxidizing atmosphere. As a result, surprisingly, the amount of calcium carbonate inside was 15, as shown in the model in Figure 2.
If the amount of quicklime is less than 15% by weight, the hole must be large to vent the gas from the outer shell of quicklime to the inside, that is, the hole must be large to release the carbon dioxide gas produced under pressure due to thermal decomposition of calcium carbonate, and if it exceeds 15% by weight, the hole must be small. discovered.
このガス抜は穴が小さいことによって、本発明に係る生
石灰粉が融鉄中に吹込まれたときは、内部に残存する炭
酸カルシウムの急激な加熱で分解発生する炭酸ガスが、
外殻の生石灰を微細に爆裂させ、融鉄との反応界面積を
著しく高め、かくして優れた脱硫性能を示すものとも推
定される。Due to the small size of the holes, when the quicklime powder according to the present invention is blown into molten iron, the carbon dioxide gas decomposed and generated by the rapid heating of the calcium carbonate remaining inside is released.
It is also presumed that the quicklime in the outer shell is finely exploded, significantly increasing the reaction interface area with molten iron, and thus exhibiting excellent desulfurization performance.
また、内部の炭酸カルシウムの量が６０重ｆｆｋ％を超
えるときは、前記したように脱硫剤として生石灰の量が
減る以外Ｋ、炭酸カルシウムの分解が吸熱反応でちり融
鉄の温度降下とのバランス上好ましくないこと、および
炭酸カルシウムの分解による炭酸ガス量が多くスプラッ
シュによる融鉄の飛散が多くなる、等で好ましくないか
らである。In addition, when the amount of internal calcium carbonate exceeds 60% by weight, in addition to the decrease in the amount of quicklime as a desulfurizing agent as described above, the decomposition of calcium carbonate is an endothermic reaction that is balanced with the temperature drop of the dust molten iron. This is because the amount of carbon dioxide gas due to the decomposition of calcium carbonate is large and the amount of molten iron is scattered due to splashing, which is undesirable.
更に、石灰質粉末を酸化性雰囲気下で流動焙焼して得ら
れる本発明の生石灰粉の粒径は、王として６０μ以下が
好ましい。本願明細書で「主として粒径６０μ以下」と
は、６０μ以下の粒度の粉末が８０重量％以上、好まし
くは９０重量％以上をいい、特に好ましくは４６μ以下
の粒度の粉本が８０重量％以上、最も好ましくは９０重
量％以上の意味で用いるものである。粒径が主として６
０μを超え粗大すぎると、ガス搬送性が低下し、吹込み
時のキャリア・ガス中の脱硫剤の濃度の変動等が大きく
なり、且つ生石灰粉の脱硫性能が十分に発揮出来ないも
のになるので好ましくない。Furthermore, the particle size of the quicklime powder of the present invention obtained by fluidized calcining of calcareous powder in an oxidizing atmosphere is preferably 60 μm or less. In the present specification, "mainly particle size 60μ or less" refers to 80% by weight or more, preferably 90% by weight or more of powder with a particle size of 60μ or less, particularly preferably 80% by weight or more of powder with a particle size of 46μ or less. , most preferably 90% by weight or more. Particle size is mainly 6
If it exceeds 0μ and is too coarse, gas transportability will decrease, fluctuations in the concentration of the desulfurizing agent in the carrier gas during injection will increase, and the desulfurization performance of quicklime powder will not be fully demonstrated. Undesirable.
本発明の融鉄の脱硫剤が、吹込み脱硫で優れたガス搬送
性、ならびに脱硫性能を発揮する理由は、それ自体が微
細粒であって重量当りの表面状が犬、きく、融鉄との接
触性に優れている外に、更Ｋ。The reason why the desulfurization agent for molten iron of the present invention exhibits excellent gas transportability and desulfurization performance in blow desulfurization is that it itself has fine particles and the surface texture per weight is comparable to that of molten iron. In addition to its excellent contact properties, it also has excellent contact properties.
前記したように微細に有効に爆裂すること、および、炭
酸カルシウムの熱分解によって発生した炭酸ガスによる
融鉄の適度の攪拌、等に基づく、種々の効果が相乗的に
作用するためと推定される。This is presumed to be due to the synergistic effect of various effects based on the effective minute explosion as described above and the appropriate stirring of the molten iron by the carbon dioxide gas generated by the thermal decomposition of calcium carbonate. .
本発明の、石灰質粉末を酸化性雰囲気で流動焙焼して得
られる生石灰粉は、吹込み脱硫法で従来の生石灰粉では
得られなかった優れた脱硫性を発揮するものであるが、
従来から知られた種々の脱硫剤及び脱硫助剤等、例えば
、カルシウムカーバイド；カルシウムシアナミド；ナト
リウム、マグネシウム、アルミニウムの酸化物、水酸化
物、炭酸塩等；カルシウムの水酸化物；ジアミド石灰；
金属の酸化物、塩化物；硼素化合物；合成樹脂粉末；脱
硫系中においてら水もしくは水素を脱離し得る成分の化
合物、等と併用することにより、更に脱硫効果を改善せ
しめることもＣきる。The quicklime powder of the present invention obtained by fluidized calcining of calcareous powder in an oxidizing atmosphere exhibits excellent desulfurization properties that cannot be obtained with conventional quicklime powder using the blow desulfurization method.
Various conventionally known desulfurization agents and desulfurization aids, such as calcium carbide; calcium cyanamide; oxides, hydroxides, carbonates of sodium, magnesium, and aluminum; calcium hydroxide; diamide lime;
The desulfurization effect can be further improved by using in combination with metal oxides and chlorides; boron compounds; synthetic resin powders; compounds with components capable of desorbing water or hydrogen in the desulfurization system.
本発明の融鉄の脱硫剤は、従来用いられた４に石灰粉と
は異なり極めて優れたガス搬送性を有するので、該生石
灰粉を単独で用いても、また前記脱硫助剤を併用して用
いても、吹込み脱硫においてバイブの閉室を生じないこ
とは勿論、脱硫剤ｆＪ（給時の脈動（バラツキ）も殆ん
ど生じることがないので、撓めて安定した脱硫ｍ業を行
うことができる６而して、本発明の融鉄の脱硫剤を、キ
ャリアがスによって融鉄中に吹込む方法としては、該脱
疏斉りを収容したホ７バーよりロータリーバルブで吹込
配管は供給する方法や圧力容ａ；内？該脱硫削を流動化
させてキャリアガスで吹込む方法（特開昭４９−３１５
１８号）等の方法が採用されるが、特に後者の方法が好
適に採用される。The desulfurizing agent for molten iron of the present invention has an extremely excellent gas transport property unlike the conventionally used lime powder, so it can be used alone or in combination with the desulfurizing aid. Even when using the desulfurizing agent fJ, it does not cause the chamber to close in the vibrator during blow desulfurization, and there is almost no pulsation (variation) during feeding, so it can be flexed to perform stable desulfurization. 6 Therefore, as a method for injecting the desulfurizing agent for molten iron of the present invention into molten iron using a carrier gas, the blowing pipe is supplied from the ho7 bar containing the desulfurizing agent with a rotary valve. A method of fluidizing the desulfurization cutting within the pressure capacity a and blowing it with a carrier gas (Japanese Patent Laid-Open No. 49-315
Methods such as No. 18) are employed, and the latter method is particularly preferably employed.
斯くして１本発明の融鉄の脱硫剤を融鉄の脱硫に用いた
場合は、脱硫性能が高いので、添加量（原単位）も少く
て済みこのためスラグ同伴等による融鉄の損失も大巾に
改善されるなど多大の利点をも有するものである。Thus, 1. When the desulfurizing agent for molten iron of the present invention is used for desulfurizing molten iron, the desulfurization performance is high, so the amount added (unit consumption) can be small, and therefore there is no loss of molten iron due to entrainment of slag, etc. It also has many advantages, including vast improvements.
次に、本発明に係る生石灰粉を石灰質粉末から製造する
流動焙焼法の詳細について説明する。Next, details of the fluidized roasting method for producing quicklime powder according to the present invention from calcareous powder will be explained.
石灰質粉末のｆｌ、！ＩＪ焙焼法に用いる熱媒体として
杜、非バインダー注、非燃焼性の不溶触性固体媒体が利
用され、例えば、生石灰、珪砂、アルミナ珪砂、クリ７
カー、石膏粒体、長石、陶石、蝋石、球石、張石、ジル
コン、ペタライト、シャモット、ムライト、コージライ
ト、シリマライト、カイヤナイト、アンダリュサイト、
静上頁岩、ケイ酸カルシウム化合物、耐火煉瓦、金属粉
末、金Ｅ酸化物粉末、ガラス粉末などを挙げることがで
きるが、好ましくは生石灰が好適に用いられる。fl of calcareous powder,! Mori, non-binder, non-combustible, insoluble solid media are used as heat carriers for IJ roasting, such as quicklime, silica sand, alumina silica sand, and chestnut 7.
Carr, gypsum granules, feldspar, pottery stone, rouseki, coccule, zircon, petalite, chamotte, mullite, cordierite, sillimarite, kyanite, andalusite,
Examples include Shizami shale, calcium silicate compounds, refractory bricks, metal powders, gold E oxide powders, and glass powders, but quicklime is preferably used.
これら熱媒体はｖＬａ層を形成し、導入されて来る原料
石灰質粉末の外殻の熱分解反応に必要な熱量を供給する
とともに、石灰質粉末の流動焙焼が不十分のうちに流動
層外へ飛び出してしまうことの防止、および生成される
生石灰粉の凝集による粒径の増大化を防止し、粒度の均
一化などの作用を行うものである。These heat carriers form a vLa layer and supply the amount of heat necessary for the thermal decomposition reaction of the outer shell of the raw material calcareous powder introduced, and also jump out of the fluidized bed before the calcareous powder is sufficiently fluidized. This function prevents the quicklime powder from forming and increasing the particle size due to agglomeration, and makes the particle size uniform.
この様な効果を十分に果し、得られる生石灰粉江優れた
脱硫性能等を付与する流動焙焼を行うためには、熱媒体
の粒径０．３〜２．０１７１１７１のものが、全媒体の
少くとも７０重量％、好ましくは８０重量％以上占める
ことが必要であり、好ましくは０．３〜ｌ、 ５ ｍｒ
ｘのものが少くとも７０重量％好ましくは８０重量％以
上占めることが望ましい。熱媒体が２−い開を超えて大
き過ぎるときは、均一な焼成の生石灰粉が得られないこ
とが屡々起こシ、また０、３ｔ＋ｍ 未満と小さ過ぎる
ときは熱媒体の流動層外への飛散が起るので好ましくな
い。In order to perform fluidized roasting that fully achieves these effects and imparts excellent desulfurization performance to the obtained quicklime powder, it is necessary to use a heating medium with a particle size of 0.3 to 2.0171171. It is necessary to account for at least 70% by weight, preferably 80% by weight or more, and preferably 0.3 to 1,5 mr.
It is desirable that x accounts for at least 70% by weight, preferably 80% by weight or more. If the heating medium is too large (more than 2 mm), it often happens that uniformly fired lime powder cannot be obtained, and if it is too small (less than 0.3 t+m), the heating medium may scatter out of the fluidized bed. This is not desirable because it causes
上記熱媒体で形成される流動層中への石灰質粉末の供給
は、熱媒体重量の０．２〜２−５倍／時でらり、好まし
くは０．５〜１，５倍／時にとると好結果が得られる。The calcareous powder is fed into the fluidized bed formed by the heating medium at a rate of 0.2 to 2-5 times the weight of the heating medium/hour, preferably 0.5 to 1.5 times/hour. Good results can be obtained.
１５倍／時を超えて多すぎると不均一に流動焙焼される
傾向が強まシ、０．２倍／時未満よ）少なすぎると、石
灰質粉末が過度に流動焙焼され、内部に残存する炭酸カ
ルシウム分が少ぐなシ、得られる生石灰粉の吹込み脱硫
に於ける脱硫性能が低下する傾向が生ずる。また、流動
層の高さとしては０．５ｍ以上、好ましくは１．５−３
．０翼の範囲にあるのがよい。If the amount is too high (more than 15 times/hour), there is a strong tendency for non-uniform fluidized roasting. If the calcium carbonate content is low, the desulfurization performance of the obtained quicklime powder during blow desulfurization tends to decrease. In addition, the height of the fluidized bed is 0.5 m or more, preferably 1.5-3 m.
．． It is better to be in the range of 0 wings.
上記の如く熱媒体の粒径が特定範囲であり、且つ、流動
焙焼炉に導入される石灰質粉末を熱媒体量に対して特定
範囲に規定し、更に、後述する特定範囲の滞留時間と燃
焼ガスの空塔速度の条件が特に重要な条件であって、こ
れによって顕著に改善されたガス搬送性ならびに脱硫性
能を発運する生石灰粉が、原料石灰質粉末よ）効果的に
得られるのでちる。As mentioned above, the particle size of the heat transfer medium is within a specific range, and the calcareous powder introduced into the fluidized torrefaction furnace is defined within a specific range with respect to the amount of heat transfer medium, and furthermore, the residence time and combustion are within a specific range as described below. The gas superficial velocity condition is a particularly important condition, as it allows quicklime powder to be effectively obtained which exhibits significantly improved gas transportability and desulfurization performance (compared to the raw calcareous powder).
燃焼ガスの空塔速度は、安定な流動層を形成させ、得ら
れる生石灰粉に粒度均一性の付与、ならびに１５重ｉチ
を超え６０重ｆチ以下の炭酸カルシウムの内部構造形成
にらずかる重要な因子でおるが、該空塔速度は１．１〜
２−７１１Ｉ／秒の範囲内にあることが必要で、好まし
くは１．２〜２．５ ｍ７秒の空塔速度が望まれる。The superficial velocity of the combustion gas allows the formation of a stable fluidized bed, imparts particle size uniformity to the resulting quicklime powder, and helps form an internal structure of calcium carbonate of more than 15 parts and less than 60 parts by weight. Although it is an important factor, the superficial velocity is 1.1~
A superficial velocity of 1.2 to 2.5 m7s is desired.
本明細書でいう「空塔速度」とは、流動焙焼炉に供給さ
れる気体（例えば空気および一酸化炭素など）が、所定
の炉内温度（例えば８５０℃）にそのまま加熱され膨張
したどきの合計供給量（＃ｈｒ）を、流動層断面ｆＲ（
、Ｉ’）で除した商（ｍ／ｈｒ）をｍ／Ｓ ｅ Ｃ単位
に換算したものである。該空塔速度１．１Ｍ秒未満と遅
すぎては生石灰粉が焼き締シの傾向が生じ脱硫性が低下
するので好ましくなく、２．７ｖ秒を超え速すぎては、
未焼成品の混入が増大するほかに粒度不均一性が増大す
るなど生じて好ましくない。In this specification, "superficial velocity" refers to the speed at which the gas (e.g., air and carbon monoxide) supplied to the fluidized torrefaction furnace is heated to a predetermined furnace temperature (e.g., 850°C) and expanded. The total supply amount (#hr) of fluidized bed cross section fR (
, I') is converted into m/S e C units. If the superficial velocity is too slow, less than 1.1 M seconds, the quicklime powder tends to sinter and the desulfurization performance is reduced, which is undesirable; if it exceeds 2.7 v seconds,
This is undesirable because not only does the contamination of unfired products increase, but also the non-uniformity of particle size increases.
特に良好な流動焙焼効果が実現されるには、以上述べた
諸条件に加えて焙焼温度が８００〜９００℃で且つ流動
層中の滞留時間が５〜２０秒であることが必要である。In order to achieve a particularly good fluidized roasting effect, in addition to the above-mentioned conditions, it is necessary that the roasting temperature be 800 to 900°C and the residence time in the fluidized bed be 5 to 20 seconds. .
焙焼温度が８００℃未満で低くすぎると焼成の不完全性
が増大し好ましくなく、９０ Ｑ Ｃｔ−超え高温すぎ
ると、過度に流動焙焼される傾向が生ずるので好ましく
ない。また、滞留時間が２０秒を超えて長すぎては脱硫
性能が低下する傾向を示し。If the roasting temperature is too low (less than 800°C), incompleteness of firing will increase, which is undesirable. If the roasting temperature is too high, exceeding 90 Q Ct-, there will be a tendency for excessive fluidized roasting to occur, which is undesirable. Furthermore, if the residence time is too long, exceeding 20 seconds, the desulfurization performance tends to decrease.
また５秒未満と短かすぎては炭酸カルシウムが内部に過
度に残存するようになるので好ましくない。On the other hand, if the heating time is too short, such as less than 5 seconds, calcium carbonate will remain excessively inside, which is not preferable.
焙焼熱源としては、−酸化炭素、天然ガス、プロパン、
都市ガス等の気体燃料、重油等の液体燃料およびコーク
ス粉等の固体燃料、望むならばこれらのものを適宜併用
して使用することができる。Roasting heat sources include - carbon oxide, natural gas, propane,
Gaseous fuel such as city gas, liquid fuel such as heavy oil, solid fuel such as coke powder, and if desired, these fuels may be used in combination as appropriate.
流動焙焼法としては、上記燃料の完全燃焼に必要な酸素
を空気の供給によって確保されるのが一般であるが、本
発明においては前記したように戯化注雰囲気で石灰質粉
末を流動焙焼する必要があ）、このためＫは空気中の酸
素量が燃料の完全燃焼に必要な理論酸素量の１．０５倍
以上、好ましくは１．１〜２．．５倍、更に好ましくは
１．１〜２．２倍であることが望ましい。これらの酸素
量の範囲、即ち、酸素量の特定の過剰下で石灰質粉末を
流動焙焼した場合、前記したように理由が明らかでない
が、生成される生石灰粉は、著しく優れたガス搬送性お
よび脱硫性能を発揮する。In the fluidized roasting method, the oxygen necessary for complete combustion of the fuel is generally secured by supplying air, but in the present invention, as described above, the calcareous powder is fluidized and roasted in an atmosphere of oxidation. Therefore, K is such that the amount of oxygen in the air is at least 1.05 times the theoretical amount of oxygen required for complete combustion of the fuel, preferably 1.1 to 2. ．． It is desirable that it is 5 times, more preferably 1.1 to 2.2 times. When calcareous powder is fluidized in these oxygen content ranges, i.e., in a specific excess of oxygen, the resulting quicklime powder has significantly superior gas transportability and Demonstrates desulfurization performance.
かくして、酸化性雰囲気下で、生石灰粉の内部に特定量
の炭酸カルシウムを含有した状態で、微細な粉に流動焙
焼された生石灰粉は、その微細な粉の状態を損うことな
く焙焼炉からキャリーオーバ一方式で取り出され捕集さ
れるが、該捕集方法としては公知の種々の方法、例えば
、キャリーオーバ一方式で排風管を通った排風と生石灰
粉は１個または数個組合されたサイクロンに導かれ、該
サイクロンで生石灰粉を捕集する方法、等を用いること
ができる。In this way, quicklime powder that has been fluidized and roasted into a fine powder in an oxidizing atmosphere with a specific amount of calcium carbonate inside it can be roasted without damaging its fine powder state. It is taken out from the furnace using the carryover method and collected, but various known methods can be used for this collection method. It is possible to use a method in which quicklime powder is collected by a combination of individual cyclones.
次に、本発明の脱硫剤の製造法における、流動焙焼法お
よび装置の基本的なものＫついて添付図面を用いて説明
する。Next, the fluidized roasting method and the basic equipment K in the method for producing a desulfurizing agent of the present invention will be explained using the attached drawings.
矛１図において、石灰質粉末、熱媒体はホッパー２．２
’よりｉ動焙焼炉本体１へ供給される。供給方式は空気
輸送方式、スクリューフィーダ方式等の輸送方式が適宜
採用される。−酸化炭素、重油、コークス等の燃料タン
ク３から送られた燃料は、フィルター６から多孔板、或
いは、多数のノズルが設けられたノズル板５等を通シ炉
底より炉頂に流れる空気によって、バーナーロ４で酸化
性雰囲気の下に燃焼し燃焼ガスとなる。炉本体１の中で
流動焙焼された生石灰粉は排風と共に、キャリーオーバ
一方式で炉頂より排風管７を通りサイクロン８で大部分
の生石灰粉が捕集され製品ホッパー１０に入る。サイク
ロン８を出た排風は、更に排風管９を通ってバックフィ
ルター（図示せず）へ導かれ、同伴する一部の生石灰粉
が取除かれる。In Figure 1, the calcareous powder and heat medium are in hopper 2.2.
' is supplied to the i-dynamic roasting furnace main body 1. As the supply method, a transportation method such as a pneumatic transportation method or a screw feeder method is appropriately adopted. - Fuel such as carbon oxide, heavy oil, coke, etc. sent from the fuel tank 3 is passed from the filter 6 through a perforated plate or a nozzle plate 5 equipped with a large number of nozzles, etc., by air flowing from the bottom of the furnace to the top of the furnace. , burns in an oxidizing atmosphere in burner rotor 4 and becomes combustion gas. The quicklime powder that has been fluidized and roasted in the furnace body 1 passes through the exhaust pipe 7 from the top of the furnace in a one-way carryover manner with the exhaust air, and most of the quicklime powder is collected by the cyclone 8 and enters the product hopper 10. The exhaust air exiting the cyclone 8 is further guided to a back filter (not shown) through an exhaust pipe 9, and some of the accompanying quicklime powder is removed.
以下、実施例、比較例によシ本発明を更に罪刑に説明す
る。The present invention will be further explained below with reference to Examples and Comparative Examples.
（流動焙焼による脱硫剤の製造）
実施例１〜５．および比較例１〜２
第１図に示した内径５ＱＱｍｍ、高さ３０００ｍ＋ａの
流動焙焼炉を用い、粒度０．２５〜１．Ｑ ｍｙｔが８
５Ｎ量チの生石灰を熱媒体とし、炉内温度７８０〜９５
０℃で（炉頂部で測定）第２表に゛示す条件でジアミド
石灰を焙焼し、サイクロンよシ生石灰粉を得た。(Production of desulfurization agent by fluidized roasting) Examples 1 to 5. Comparative Examples 1 and 2 Using a fluidized roasting furnace with an inner diameter of 5QQmm and a height of 3000m+a shown in FIG. 1, a particle size of 0.25-1. Q myt is 8
Using 5N quicklime as a heat medium, the furnace temperature is 780-95.
Diamide lime was roasted at 0° C. (measured at the top of the furnace) under the conditions shown in Table 2 to obtain quicklime powder in a cyclone.
使用したジアミド石灰の化学組成および粒度分布は１５
１表のものである。The chemical composition and particle size distribution of the diamide lime used was 15
This is from Table 1.
第 １ 表
ｆ：１５２表に示す流動焙焼条件で得られた生石灰粉の
、ＣｕＯ２内部のＣａ ＣＯｓ、ＣおよびＳ ＋ ０２
、Ａ ＬＯ、、Ｆｅ２Ｏ，、Ｍｇ０９のその他の化学組
成および粒度分布を第３表に示す。1st Table f: Ca COs, C and S + 02 inside CuO2 of quicklime powder obtained under the fluidized roasting conditions shown in Table 152
, ALO, , Fe2O, , and other chemical compositions and particle size distributions of Mg09 are shown in Table 3.
実施例１〜５および比較例１〜２で得られた生石灰粉の
脱硫性能およびガス搬送性を試験した結果を実施例６〜
１０１および比較例３〜４に示した。The results of testing the desulfurization performance and gas transportability of quicklime powder obtained in Examples 1 to 5 and Comparative Examples 1 to 2 are shown in Examples 6 to 5.
101 and Comparative Examples 3 and 4.
（脱硫剤の性能試験）
実施例６〜１０および比較例３〜４
硫ｆ含有見Ｑ、０３７〜０．０４５％の溶銑２７０〜３
３０Ｔ充填された３５０Ｔ容量のトービーＦｌ／−）”
ルニ、！ｍｆ昭４９−３１５１８号に記載の吹込み装置
で、乾燥窒素ガスをキャリアが又として第４表に示す脱
硫剤を吹込速度８０〜１５０ｋｇ／分の条件でランスか
ら溶銑中に吹き込み脱硫を行った。(Performance test of desulfurization agent) Examples 6 to 10 and Comparative Examples 3 to 4 Hot metal with sulfur content Q, 037 to 0.045% 270 to 3
30T filled 350T capacity Toby Fl/-)”
Luni! Using the blowing device described in MF No. 49-31518, desulfurization was carried out by blowing the desulfurizing agent shown in Table 4 into the hot metal from a lance at a blowing rate of 80 to 150 kg/min using dry nitrogen gas as a carrier. .
結果は第４表に示す６ 第４表中に用いた用語の意味は次の通りである。The results are shown in Table 4.6 The meanings of the terms used in Table 4 are as follows.
（ロ）キャリア〃ス／ｒＢｔ硫剤；
（ハ）吹込圧：脱硫剤粉末をキャリアガスに同伴させ、
溶銑中に吹込み時の、吐出部に
接続されるキャリアガスの圧力＜ｋｇ／ａｍ２）（特開
昭４９−３１５１８号明細書のｆｊＳ２図に於いて吐出
孔４に接続とれる相対に低い圧力Ｐ、に該当す
る。）
（ニ）脱硫性能：Ｓ、＝脱硫前の溶銑中の硫黄含有率（
％）
Ｓ２＝脱硫後の溶銑中の硫黄含有率
（％）
比較例 ５
工業用カーバイドの原料生石灰で化学組成がＣａ Ｃ０
，３重量％、Ｃａ０９１重量％、粒度１００μ下が５０
重量％の生石灰粉を用いた以外は前記実施例１０〜１４
に準じて脱硫を行ったが、キャリアガス／生石灰粉を７
ＯＮｆｆｉ／ｋｇ以上にしても吹込み不能であった。(b) Carrier gas/rBt sulfur agent; (c) Blow pressure: Desulfurizing agent powder is entrained in carrier gas,
Pressure of the carrier gas connected to the discharge part when blowing into hot metal <kg/am2) (relatively low pressure P connected to the discharge hole 4 in the fjS2 diagram of JP-A No. 49-31518) ) (d) Desulfurization performance: S, = sulfur content in hot metal before desulfurization (
%) S2 = Sulfur content in hot metal after desulfurization (%) Comparative example 5 Raw lime for industrial carbide with chemical composition Ca C0
, 3% by weight, Ca091% by weight, particle size below 100μ is 50
Examples 10 to 14 above except that quicklime powder of % by weight was used.
Desulfurization was carried out according to
Even if it exceeded ONffi/kg, it was impossible to inject.
第４表に示すように本発明の脱硫剤は脱硫性能、〃ス搬
送性に於いて優れた性能を示した。As shown in Table 4, the desulfurization agent of the present invention exhibited excellent performance in desulfurization performance and gas transportability.
第１図は、本発明の酸化性雰囲気下で石灰質粉末を流動
焙焼する装置の原理を示す図であり、１は炉本体、２は
原料ホッパー、２′は熱媒体用のホッパー、３は燃料タ
ンク、４はバーナーロ、５は多孔板、６は空気用フィル
ター、７は排気管、８はサイクロン、９は排風管、１０
は製品ホッパーを示す。
ｆｊＳ２図は、酸化性雰囲気下でジアミド石灰を過度に
流動焙焼した、内部に炭酸カルシツムを約１０重量％含
有する生石灰粉の、生石灰外殻部から内側に向は生成し
たガス抜は穴の断面状態を模型的に示すもので、２０は
生石灰粉外殻部、２１はガス抜は穴である。
特許出願人 川崎５！鐵株式会社
外２名FIG. 1 is a diagram showing the principle of the apparatus for fluidized torrefaction of calcareous powder in an oxidizing atmosphere according to the present invention, in which 1 is the furnace body, 2 is a raw material hopper, 2' is a hopper for heat medium, and 3 is a Fuel tank, 4 is a burner, 5 is a perforated plate, 6 is an air filter, 7 is an exhaust pipe, 8 is a cyclone, 9 is an exhaust pipe, 10
indicates the product hopper. The fjS2 diagram shows the holes in the quicklime powder, which contains about 10% by weight of calcium carbonate, produced by excessive fluidized roasting of diamide lime in an oxidizing atmosphere. The cross-sectional state is schematically shown, and 20 is a quicklime powder outer shell, and 21 is a gas vent hole. Patent applicant Kawasaki 5! 2 people from outside Tetsu Co., Ltd.
Claims (4)
れる生石灰粉を含有してなる脱硫剤であって、該生石灰
粉はその内部に炭酸カルシウムを１５重量％超え６０重
量％以下含有し且つその粒径が主として６０μ以下であ
る吹込み脱硫用の融鉄の脱硫剤。(1) A desulfurizing agent containing quicklime powder obtained by fluidized roasting of calcareous powder in an oxidizing atmosphere, wherein the quicklime powder contains more than 15% by weight and less than 60% by weight of calcium carbonate. A desulfurizing agent for molten iron for blow desulfurization, the particle size of which is mainly 60μ or less.
第１項記載の吹込み脱硫用の融鉄の脱硫剤。(2) A desulfurizing agent for molten iron for blow desulfurization according to claim 1, wherein the calcareous powder is diamide lime.
粉末を時間当り熱媒体重量の０．２〜２．５倍量供給し
、燃焼ガスの空塔速度１．１〜２．７ｍ／ｓｅｃの酸化
性雰囲気下で流動焙焼し、且つ流動焙焼して得られる生
石灰粉をキャリーオーバ方式で取り出す方法おいて、焙
焼温度８００〜９００℃、滞留時間５〜２０秒であるこ
とを特徴とする、生石灰粉を含有してなる脱硫剤であっ
て、該生石灰粉はその内部に炭酸カルシウム１５重量％
超え６０重量％以下含有し且つその粒径が主として６０
μ以下である吹込み脱硫用の融鉄の脱硫剤の製造法。(3) Using a heating medium with a particle size of 0.3 to 2.0 mm, calcareous powder is supplied in an amount of 0.2 to 2.5 times the weight of the heating medium per hour, and the superficial velocity of the combustion gas is 1.1 to 2. In a method of fluidized roasting in an oxidizing atmosphere of .7 m/sec and taking out quicklime powder obtained by fluidized roasting by a carryover method, the roasting temperature is 800 to 900 ° C. and the residence time is 5 to 20 seconds. A desulfurizing agent containing quicklime powder, characterized in that the quicklime powder contains 15% by weight of calcium carbonate therein.
It contains more than 60% by weight and the particle size is mainly 60% by weight.
A method for producing a desulfurizing agent for molten iron for blow desulfurization that is less than μ.
第３項記載の吹込み脱硫用の融鉄の脱硫剤の製造法。(4) The method for producing a desulfurizing agent for molten iron for blow desulfurization according to claim 3, wherein the calcareous powder is diamide lime.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19598185A JPS6169911A (en) | 1985-09-06 | 1985-09-06 | Desulfurizing material for molten iron and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19598185A JPS6169911A (en) | 1985-09-06 | 1985-09-06 | Desulfurizing material for molten iron and its production |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10065282A Division JPS58217619A (en) | 1982-06-14 | 1982-06-14 | Desulfurizing agent for molten iron and manufacture thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6169911A true JPS6169911A (en) | 1986-04-10 |
| JPH0440406B2 JPH0440406B2 (en) | 1992-07-02 |
Family
ID=16350221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19598185A Granted JPS6169911A (en) | 1985-09-06 | 1985-09-06 | Desulfurizing material for molten iron and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6169911A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56158827A (en) * | 1980-05-10 | 1981-12-07 | Nippon Carbide Ind Co Ltd | Powdered composition for desulfurizing agent |
| JPS56163213A (en) * | 1980-05-20 | 1981-12-15 | Nippon Carbide Ind Co Ltd | Desulfurizer powder composition for molten iron |
| JPS5726116A (en) * | 1980-06-18 | 1982-02-12 | Sueddeutsche Kalkstickstoff | Desulfurization agent and desulfurizing of molten iron |
-
1985
- 1985-09-06 JP JP19598185A patent/JPS6169911A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56158827A (en) * | 1980-05-10 | 1981-12-07 | Nippon Carbide Ind Co Ltd | Powdered composition for desulfurizing agent |
| JPS56163213A (en) * | 1980-05-20 | 1981-12-15 | Nippon Carbide Ind Co Ltd | Desulfurizer powder composition for molten iron |
| JPS5726116A (en) * | 1980-06-18 | 1982-02-12 | Sueddeutsche Kalkstickstoff | Desulfurization agent and desulfurizing of molten iron |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0440406B2 (en) | 1992-07-02 |
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