JP2004076088A - Method for recycling desulfurization slag - Google Patents

Method for recycling desulfurization slag Download PDF

Info

Publication number
JP2004076088A
JP2004076088A JP2002237358A JP2002237358A JP2004076088A JP 2004076088 A JP2004076088 A JP 2004076088A JP 2002237358 A JP2002237358 A JP 2002237358A JP 2002237358 A JP2002237358 A JP 2002237358A JP 2004076088 A JP2004076088 A JP 2004076088A
Authority
JP
Japan
Prior art keywords
desulfurization
slag
hot metal
desulfurizing agent
desulfurized
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
Application number
JP2002237358A
Other languages
Japanese (ja)
Other versions
JP3960164B2 (en
Inventor
Yoshiyuki Tanaka
田中 芳幸
Itsuo Miyazono
宮園 五男
Masaru Washio
鷲尾 勝
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.)
JFE Steel Corp
Original Assignee
JFE Steel Corp
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 JFE Steel Corp filed Critical JFE Steel Corp
Priority to JP2002237358A priority Critical patent/JP3960164B2/en
Publication of JP2004076088A publication Critical patent/JP2004076088A/en
Application granted granted Critical
Publication of JP3960164B2 publication Critical patent/JP3960164B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Landscapes

  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simple method for recycling desulfurization slag without modifying facilities. <P>SOLUTION: This method includes, in a step of previously keeping molten pig iron to be charged into a converter in a refining container, and desulfurizing the molten iron by charging and stirring a lime-based desulfurizing agent, charging the slag in a high temperature, which has been produced in the above desulfurization step, has been separated from the above molten pig iron, and has been collected in the refining container, to the molten pig iron in the refining container for desulfurization, as a part of the desulfurizing agent.In the above method, the above refining container is preferably a hot-metal ladle, and the stirring is preferably mechanically performed. <P>COPYRIGHT: (C)2004,JPO

Description

【0001】
【発明の属する技術分野】
本発明は、脱硫スラグの再利用方法に係わり、詳しくは、転炉で脱炭精錬される溶銑は、溶銑予備処理と称し、転炉へ装入される前に予め石灰系脱硫剤の投入と攪拌により脱硫されるが、その際発生したスラグ(以下、脱硫スラグという)を再度同じ脱硫工程に脱硫剤の一部として再利用する技術に関する。
【0002】
【従来の技術】
転炉スラグ等は、造滓剤として再度利用されているが(特許公報1参照)、溶銑予備処理の脱硫工程で発生する脱硫スラグは、硫黄含有量が1.2質量%程度と高く、一般的な精錬スラグの用途(例えば、路盤材等の土木・建築用材料等)に適さない。そのため、有効な使用先が無く、製鉄所内に積み上げて放置されている。
【0003】
【特許公報1】
特開平4−120209号公報(2頁、右欄の4行〜19行)
ところが、上記脱硫工程で使用する脱硫剤は、石灰系物質を主体としているので、転炉スラグと比べてCaO含有量が非常に高く、その再利用が望ましい。そこで、発明者は、放置されている脱硫スラグを脱硫剤の一部として混合し、該脱硫工程に利用することを試みた。図4は、脱硫スラグを脱硫剤として再利用した実験内容を示すもので、(A)は脱硫スラグの処理形態を示し、10は散水冷却で常温まで冷却する場合を、11は散水を行わずに放置して常温まで冷却する場合を示している。すなわち、脱硫スラグは、溶銑鍋等の反応容器から排滓された後、脱硫場よりスラグ置場へ搬送され、図4に(A)で示したように、散水あるいは非散水により常温まで冷却される。この一旦冷却された脱硫スラグは、図4の(B)に示すように、袋詰めされて脱硫場へ運搬し、脱硫剤の代用品として再利用するのである。なお、この際の脱硫は、図4(C)に示すように、溶銑中に撹拌翼を浸漬して回転させ、脱硫剤を添加する所謂「インペラ脱硫」を採用した。
【0004】
この実験の結果を図5に示す。図5での○印は、石灰系脱硫剤を使用した時のCaO換算の脱硫剤原単位(Total.CaO(kg/t))と脱硫率との関係を示したものである。通常、脱硫スラグは、約60質量%のCaO分を含んでいるので、このCaO分が脱硫剤として寄与するはずである。ところが、図5に□印や△印で示すように、同じ脱硫剤原単位で実験したのに、Total.CaOが2kg/tのレベルでは反応効率が低く、バラツキも大きくなっていた。また、4kg/tのレベルでも同様の結果であり、■印や▲印で示すように、石灰系脱硫剤と再利用脱硫スラグを併用した実験でも、脱硫率ははかばかしいものでなかった。なお、□印は散水冷却を施した脱硫スラグを、△印は非散水冷却のスラグを、■印は散水冷却を施した脱硫スラグと石灰系脱硫剤の併用を、▲印は非散水冷却の脱硫スラグと石灰系脱硫剤の併用データである。
【0005】
脱硫スラグの溶銑脱硫工程への再利用は、上記のような問題がある他、一旦脱硫場よりスラグ置場に移動し、冷却処理後に再度脱硫場へ搬送するので、運搬、処理に費用がかかり、その分だけ再利用に必要なコストが高くなるという問題があり、直ちに実用化し難いのが現状である。
【0006】
【発明が解決しようとする課題】
本発明は、かかる事情に鑑み、設備改造することなく、簡便で安価な脱硫スラグの再利用方法を提供することを目的としている。
【0007】
【課題を解決するための手段】
発明者は、上記目的を達成するため鋭意研究を重ね、その成果を本発明に具現化した。
【0008】
すなわち、本発明は、転炉装入前の溶銑を予め精錬容器に保持し、石灰系脱硫剤の投入と攪拌により該溶銑の脱硫を行うに際して、前記脱硫で発生し、前記溶銑と分離して精錬容器より排出した高温のスラグを、脱硫を行う精錬容器中の溶銑へ、その脱硫剤の一部として投入することを特徴とする脱硫スラグの再利用方法である。この場合、前記精錬容器が溶銑鍋であり、前記溶銑の攪拌は機械的に行うのが好ましい。
【0009】
本発明によれば、先の脱硫処理で発生したスラグを、次回の脱硫処理に脱硫剤の一部として再利用するようにしたので、脱硫スラグの風化は起きず、且つ長距離を搬送する必要がなくなる。また、高温のまま利用するので、熱の有効利用にもなる。
【0010】
【発明の実施の形態】
以下、発明をなすに至った経緯をまじえ、本発明の実施の形態を説明する。
【0011】
まず、発明者は、脱硫スラグを溶銑の脱硫工程に再利用した際の脱硫効率の低下について探求し、図5に係る脱硫率の低い原因は、一旦冷却された脱硫スラグのCaO分が風化して、Ca(OH)やCaCOに変質していることにあると知見した。
【0012】
そこで、発明者は、脱硫スラグがその冷却前後で含有する成分に変化が生じるかどうかを調査するため、冷却前及びスラグ置場で放置、冷却された後のスラグについて成分分析を行った。その結果、表1に示すように、スラグ中に存在する未溶融CaO(記号F.CaO:所謂フリーライム)の含有率は、冷却前の方が冷却後のものより2倍多いことが確認され、この未溶融CaOの含有率が高いほど脱硫処理で再利用する時には、より有効に寄与すると考えた。
【0013】
【表1】

Figure 2004076088
【0014】
また、スラグ中の未溶融CaOが冷却されて、Ca(OH)やCaCOに変化する前に次回の溶銑脱硫に使用すれば、該未溶融CaOは脱硫反応(CaO+S→CaS+O)に有効に寄与することが期待できる。さらに、脱硫反応は、下記式で表されるS分配比(記号:L、スラグ中Sの質量%/溶銑中Sの質量%)より明らかなように、温度が高いほど進行することは自明である。
【0015】
logL=logC−loga+logf−938/T+1.33
ここで、C:スラグ中のS濃度、a:溶銑中のS活量、f:活量係数、T:溶銑温度
そこで、発明者は、脱硫スラグを一旦冷却してから次回の溶銑脱硫に利用するよりも、脱硫を行った精錬容器から排出された後のまだ高温状態(例えば、500℃以上)にあるものを利用すれば、溶銑温度の低下防止にもつながり、脱硫反応が起きる反応サイトの温度は高く、前記S分配比が向上すると考え、本発明を完成させたのである。
【0016】
その具体的な本発明の実施は、図1に示す手順を繰り返すことで行われる。つまり、
第1段階:除滓場2に配置してある滓鍋3とは別に、空の溶銑鍋1を脱硫スラグの回収用の鍋として置く。
第2段階:溶銑脱硫が終了し、まだ溶銑及び脱硫スラグを保持した状態の精錬容器4を脱硫場(図示せず)から除滓場2へ搬送し(トラック、クレーン等の利用)、該精錬容器4内のまだ高温状態の脱硫スラグ5を前記スラグ回収用の溶銑鍋1に掻き出す。
第3段階:該スラグ回収用の溶銑鍋1に掻き出された脱硫スラグ5を、次回の脱硫準備のため、別の精錬容器4に保持した溶銑へ投入する。
【0017】
なお、前記スラグ回収用の溶銑鍋1に掻き出された脱硫スラグ5の精錬容器4への投入は、スラグ回収用の溶銑鍋1を傾動して行うことができ、当該スラグ回収用の溶銑鍋1から出てくる溶融状態の脱硫スラグ、あるいは該溶融状態の脱硫スラグに伴われる高温の凝固した脱硫スラグが脱硫剤として再利用できるのである。要は、脱硫スラグが、水和反応を生じることのない高温領域にある段階で再利用を行う。
第4段階:この投入で空になったスラグ回収用の溶銑鍋1を、前記第1段階の滓鍋3前の位置へ戻す。
【0018】
この場合、前記掻き出された脱硫スラグ5は秤量され、次回の脱硫に必要なCaO分を満たしているかどうか判断される。そして、満たしている場合は、新たな脱硫剤を添加することなく次回の脱硫が行われるが、不足している場合が多いので、次回の脱硫が行われる溶銑には、脱硫剤が追加される。すなわち、本発明の脱硫スラグの溶銑脱硫への再利用では、脱硫スラグ単独での脱硫への再利用、あるいは再利用する脱硫スラグに別途脱硫剤を加えて使用することが可能であり、制約はない。また、脱硫スラグを溶銑鍋1に掻き出し、次回の脱硫時に脱硫剤として再利用することで説明しているが、複数回の脱硫過程で発生する脱硫スラグを同一の溶銑鍋1に順次掻き出して溶銑鍋1に貯え、貯えた高温のスラグを、次回及び次回以降の脱硫時の脱硫剤として再利用することもできる。さらに、貯えた脱硫スラグを保熱あるいは加熱して高温状態に維持して再利用することも可能である。 なお、本発明の実施では、図1において脱硫スラグの回収用鍋に溶銑鍋を利用したが、掻き出される脱硫スラグを回収できる容器であれば、いかなるものも利用できる。また、前記脱硫スラグの回収用鍋として溶銑鍋を使用する場合は、本発明の脱硫実施に利用する精錬容器4として、脱硫スラグの回収用と同様、溶銑鍋を利用するのが良い。脱硫処理のコストを安価にするには、既存設備の利用が有利だからである。例えば、脱硫に供した溶銑鍋の地金付き等を手入れした後に、脱硫スラグの回収鍋として使用し、脱硫スラグの回収に伴う該溶銑鍋の温度上昇(所謂、着熱)を待って、その溶銑鍋を受銑用に供するため加熱し、加熱昇温した溶銑鍋を脱硫を行うために溶銑を受ける溶銑鍋として循環使用する等、溶銑鍋の循環使用による費用削減及び溶銑鍋手入れから溶銑鍋を高温に加熱する加熱操作時の費用低減も実現でき、脱硫スラグの再利用に伴う大きな経済効果と共に、実施に伴う費用の安価化が達成できるという大きな利点がある。
【0019】
なお、溶銑鍋を使用する脱硫では、溶銑の撹拌には、図示していないが、溶銑に浸漬して使用するインペラ等の機械的な撹拌手段を用いることが好適である。
【0020】
【実施例】
製鋼工場で、転炉へ装入する前の溶銑予備処理として脱硫処理を多数チャージ実施した。その際、本発明に係る脱硫スラグの再利用方法を実施し、その結果を従来の脱硫スラグを利用しない場合での結果と比較した。なお、精錬容器4及び脱硫スラグ回収用の容器には、溶銑保持能力が180トンの溶銑鍋を使用した。また、脱硫処理としては、溶銑に脱硫剤を添加し、溶銑をインペラ式の攪拌手段で撹拌して脱硫する機械撹拌式脱硫方法を適用した。脱硫剤としては、必要に応じて成分が、CaO95質量%の石灰系脱硫剤を使用した。
【0021】
まず、図2に、本発明に係る脱硫スラグの再利用方法(リサイクル有り)及び従来法(リサイクル無し)を実施して得た溶銑中の実績S濃度と目標S濃度との差の度数分布を示す。図2より、本発明を実施しても従来法を実施した場合と同様な度数分布になっており、脱硫不良がおきていないことが明らかである。なお、脱硫の成果は、(実績S濃度―目標S濃度)×10−3で判断する。 また、図3に、脱硫スラグの使用量を除いた脱硫剤原単位(kg/t)と脱硫率(ln(S/S)との関係を示す。ここで、Sは、脱硫開始前の溶銑の硫黄濃度、Sは、脱硫後の溶銑の硫黄濃度である。図3より、○印で示す従来の脱硫剤の使用状況が脱硫スラグの再利用後は●印に変わっており、脱硫率が1.5〜2・5のところで比較すると、本発明の実施で、脱硫処理のために添加する脱硫剤を、脱硫スラグの再利用で従来より半減できたことが明らかである。
【0022】
【発明の効果】
以上述べたように、本発明により、先の脱硫処理で発生したスラグを、冷却することなく次回の脱硫処理に脱硫剤の一部として再利用するようにした。その結果、脱硫スラグの風化は起きず、脱硫スラグを脱硫剤として再利用することが可能となった。また、高温のまま利用するので、熱の有効利用にもなる。
【図面の簡単な説明】
【図1】本発明に係る脱硫スラグの再利用方法を説明する概念図である。
【図2】本発明に係る脱硫スラグの再利用方法(リサイクル有り)及び従来法(リサイクル無し)を実施して得た溶銑中の実績S濃度と目標S濃度との差の度数分布を示す図である。
【図3】脱硫スラグの使用量を除いた脱硫剤原単位(kg/t)と脱硫率(ln(S/S))との関係を示す図である。
【図4】本発明をなす根拠になった脱硫スラグの冷間再利用実験の内容を説明するフロー図である。
【図5】図4の実験結果を示す図である。
【符号の説明】
1  脱硫スラグ回収用の溶銑鍋
2  除滓場
3  滓鍋
4  精錬容器
5  脱硫スラグ
6  脱硫場への方向を示す矢印[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for reusing desulfurized slag, specifically, hot metal that is decarburized and refined in a converter is referred to as hot metal pretreatment, and a lime-based desulfurizing agent is charged before being charged into the converter. The present invention relates to a technique in which slag generated at that time (hereinafter, referred to as desulfurization slag) is reused as a part of a desulfurizing agent in the same desulfurization step.
[0002]
[Prior art]
Converter slag and the like are reused as a slag-making agent (see Patent Publication 1). However, desulfurized slag generated in the desulfurization step of hot metal pretreatment has a high sulfur content of about 1.2% by mass. It is not suitable for typical refining slag applications (for example, civil engineering and construction materials such as roadbed materials). Therefore, there is no effective place to use it, and it is piled up and left in steelworks.
[0003]
[Patent Publication 1]
JP-A-4-120209 (page 2, right column, lines 4 to 19)
However, since the desulfurizing agent used in the above desulfurization step is mainly composed of a lime-based material, the CaO content is much higher than that of the converter slag, and its reuse is desirable. Then, the inventor tried to mix the desulfurized slag that had been left as a part of the desulfurizing agent and use it in the desulfurization step. FIG. 4 shows the contents of an experiment in which desulfurized slag was reused as a desulfurizing agent. FIG. 4 (A) shows a treatment form of desulfurized slag, 10 shows a case of cooling to normal temperature by water cooling, and 11 shows no water spray. And cooling to room temperature. That is, the desulfurized slag is discharged from a reaction vessel such as a hot metal ladle and then conveyed from the desulfurization plant to the slag storage site, and cooled to room temperature by watering or non-watering as shown in FIG. . The once cooled desulfurized slag is packed in a bag, transported to a desulfurization plant, and reused as a substitute for a desulfurizing agent, as shown in FIG. 4 (B). In this case, as shown in FIG. 4C, so-called "impeller desulfurization" in which a stirring blade is immersed in hot metal, rotated and a desulfurizing agent is added, as shown in FIG.
[0004]
The result of this experiment is shown in FIG. The circles in FIG. 5 indicate the relationship between the desulfurizing agent basic unit (Total.CaO (kg / t)) in terms of CaO and the desulfurization rate when a lime-based desulfurizing agent was used. Usually, the desulfurized slag contains about 60% by mass of CaO, and this CaO should contribute as a desulfurizing agent. However, as shown by the marks □ and Δ in FIG. 5, the experiment was performed with the same unit of desulfurizing agent. At a CaO level of 2 kg / t, the reaction efficiency was low and the variation was large. Similar results were obtained even at the level of 4 kg / t. As shown by the symbols ■ and ▲, the desulfurization rate was not ridiculous even in the experiment using the lime-based desulfurizing agent and the recycled desulfurization slag in combination. . In addition, □ indicates desulfurized slag with water spray cooling, △ indicates non-water cooled slag, ■ indicates combined use of desulfurized slag with water spray cooled and lime-based desulfurizing agent, and ▲ indicates non-water cooled slag. It is combined data of desulfurization slag and lime-based desulfurization agent.
[0005]
Reuse of desulfurized slag in the hot metal desulfurization process has the above-mentioned problems.Besides, once it is moved from the desulfurization plant to the slag storage site, and then transported to the desulfurization plant again after the cooling process, transportation and treatment are expensive. There is a problem that the cost required for reuse increases by that much, and it is difficult to put it to practical use immediately.
[0006]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and has as its object to provide a simple and inexpensive method for reusing desulfurized slag without equipment modification.
[0007]
[Means for Solving the Problems]
The inventor conducted intensive research to achieve the above object, and realized the results in the present invention.
[0008]
That is, the present invention holds the hot metal before the converter is charged in the refining vessel in advance, and when desulfurizing the hot metal by charging and stirring a lime-based desulfurizing agent, the hot metal is generated in the desulfurization and separated from the hot metal. This is a method for reusing desulfurized slag, wherein high-temperature slag discharged from a smelting vessel is charged as a part of a desulfurizing agent to hot metal in a smelting vessel for desulfurization. In this case, it is preferable that the refining vessel is a hot metal pot and the hot metal is mechanically stirred.
[0009]
According to the present invention, the slag generated in the previous desulfurization treatment is reused as a part of the desulfurization agent in the next desulfurization treatment, so that weathering of the desulfurization slag does not occur and it is necessary to transport the slag over a long distance. Disappears. In addition, since the heat is used at a high temperature, the heat is effectively used.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described, taking into account the circumstances that led to the invention.
[0011]
First, the inventor searched for a decrease in desulfurization efficiency when the desulfurized slag was reused in the desulfurization step of hot metal, and the cause of the low desulfurization rate according to FIG. 5 was that the CaO content of the once cooled desulfurized slag was weathered. Thus, it was found that Ca (OH) 2 and CaCO 3 were altered.
[0012]
In order to investigate whether or not the components contained in the desulfurized slag before and after cooling change, the inventor performed component analysis on the slag before being cooled and after being left and cooled in the slag storage. As a result, as shown in Table 1, it was confirmed that the content of unmelted CaO (symbol F. CaO: so-called free lime) present in the slag was twice as high before cooling as compared with that after cooling. It was considered that the higher the content of the unmelted CaO, the more effectively it would contribute to reuse in desulfurization treatment.
[0013]
[Table 1]
Figure 2004076088
[0014]
Further, if unmelted CaO in the slag is cooled and used for the next hot metal desulfurization before changing to Ca (OH) 2 or CaCO 3 , the unmelted CaO is effectively used for the desulfurization reaction (CaO + S → CaS + O). We can expect to contribute. Further, as is clear from the S distribution ratio (symbol: L s , mass% of S in slag / mass% of S in hot metal), the desulfurization reaction is self-evidently higher as the temperature is higher. It is.
[0015]
logL s = logC s -loga o + logf s -938 / T + 1.33
Here, C s: S concentration in the slag, a o: S activity in the hot metal, f s: activity coefficient, T: molten iron temperature Therefore, the inventors next hot metal after once cooling the desulfurization slag Rather than using it for desulfurization, using a material that is still in a high temperature state (for example, 500 ° C. or higher) after being discharged from the refining vessel that has undergone desulfurization also leads to prevention of a drop in hot metal temperature and a desulfurization reaction occurs. The present invention was completed on the assumption that the temperature of the reaction site was high and the S distribution ratio was improved.
[0016]
The specific implementation of the present invention is performed by repeating the procedure shown in FIG. That is,
1st stage: Separately from the slag pot 3 arrange | positioned in the slag removal place 2, the empty hot metal pot 1 is set as a pot for collection | recovery of a desulfurization slag.
Second stage: The hot metal desulfurization is completed, and the refining vessel 4 holding the hot metal and the desulfurization slag is transported from a desulfurization plant (not shown) to the slag removal plant 2 (using a truck, a crane, etc.), and the refining is performed. The desulfurized slag 5 in the still high temperature state in the container 4 is scraped out into the hot metal pot 1 for slag recovery.
Third stage: The desulfurized slag 5 scraped into the hot metal ladle 1 for collecting slag is poured into hot metal held in another refining vessel 4 in preparation for the next desulfurization.
[0017]
The desulfurization slag 5 scraped by the hot metal ladle 1 for collecting slag can be charged into the refining vessel 4 by tilting the hot metal ladle 1 for collecting slag. The molten desulfurized slag coming out of 1 or the high-temperature solidified desulfurized slag accompanying the molten desulfurized slag can be reused as a desulfurizing agent. In short, the desulfurization slag is reused at a stage where the hydration reaction does not occur in a high temperature region.
Fourth step: The slag collecting hot metal pot 1 emptied by this charging is returned to the position before the slag pot 3 in the first step.
[0018]
In this case, the scraped-out desulfurized slag 5 is weighed, and it is determined whether or not the CaO content required for the next desulfurization is satisfied. Then, if it is satisfied, the next desulfurization is performed without adding a new desulfurization agent, but since it is often insufficient, the desulfurization agent is added to the hot metal where the next desulfurization is performed . That is, in the reuse of the desulfurized slag of the present invention for hot metal desulfurization, it is possible to reuse the desulfurized slag alone for desulfurization, or to add a desulfurizing agent separately to the desulfurized slag to be reused. Absent. Also, it is described that the desulfurized slag is scraped out to the hot metal pot 1 and reused as a desulfurizing agent at the next desulfurization. The high-temperature slag stored in the pan 1 can be reused as a desulfurizing agent at the next and subsequent desulfurization. Further, the stored desulfurized slag can be reused while keeping it at a high temperature by heat retention or heating. In the practice of the present invention, a hot metal pot was used as the desulfurization slag recovery pot in FIG. 1, but any vessel can be used as long as the scraped-out desulfurization slag can be recovered. When a hot metal pot is used as the desulfurization slag recovery pot, it is preferable to use a hot metal pot as the refining vessel 4 used for performing the desulfurization of the present invention, as in the case of the desulfurization slag recovery. This is because the use of existing equipment is advantageous for reducing the cost of desulfurization treatment. For example, after treating the hot metal pot provided with metal for the desulfurization, it is used as a recovery pan for desulfurization slag, and waits for the temperature rise (so-called heat generation) of the hot metal pot accompanying the recovery of the desulfurization slag. The hot metal pot is heated to be used for receiving the hot metal, and the heated hot metal pot is used as a hot metal pot for receiving hot metal to perform desulfurization. It is also possible to realize a reduction in cost at the time of a heating operation for heating the slag to a high temperature, and there is a great advantage that the cost reduction due to the implementation can be achieved together with a great economic effect associated with the reuse of the desulfurized slag.
[0019]
In the desulfurization using a hot metal pot, although not shown, it is preferable to use a mechanical stirring means such as an impeller which is immersed in the hot metal and used for stirring the hot metal.
[0020]
【Example】
At the steelmaking plant, a number of desulfurization treatments were charged as hot metal pretreatment before charging the converter. At that time, the method for reusing desulfurized slag according to the present invention was implemented, and the results were compared with the results obtained when conventional desulfurized slag was not used. In addition, the hot metal holding capacity of 180 tons was used for the refining vessel 4 and the vessel for desulfurization slag recovery. As the desulfurization treatment, a mechanical stirring type desulfurization method in which a desulfurizing agent was added to hot metal and the hot metal was stirred by an impeller type stirring means to desulfurize the hot metal was used. As the desulfurizing agent, a lime-based desulfurizing agent containing 95% by mass of CaO was used as necessary.
[0021]
First, FIG. 2 shows the frequency distribution of the difference between the actual S concentration and the target S concentration in the hot metal obtained by performing the method for reusing desulfurized slag (with recycling) and the conventional method (without recycling) according to the present invention. Show. FIG. 2 shows that even when the present invention is carried out, the frequency distribution is the same as when the conventional method is carried out, and it is clear that no desulfurization failure occurs. The result of desulfurization is determined by (actual S concentration-target S concentration) × 10 −3 . 3 shows the relationship between the desulfurizing agent basic unit (kg / t) excluding the amount of desulfurized slag used and the desulfurization rate (ln (S 0 / S f ), where S 0 is the start of desulfurization. sulfur concentration before the molten pig iron, S f is a sulfur concentration molten iron after desulfurization. from FIG. 3, after reuse of usage desulfurization slag of a conventional desulfurizing agent indicated by ○ marks is changed to mark ● Comparing at a desulfurization rate of 1.5 to 2.5, it is clear that in the practice of the present invention, the desulfurizing agent added for the desulfurization treatment could be reduced by half by recycling the desulfurized slag.
[0022]
【The invention's effect】
As described above, according to the present invention, the slag generated in the previous desulfurization treatment is reused as a part of the desulfurization agent in the next desulfurization treatment without cooling. As a result, the weathering of the desulfurized slag did not occur, and the desulfurized slag could be reused as a desulfurizing agent. In addition, since the heat is used at a high temperature, the heat is effectively used.
[Brief description of the drawings]
FIG. 1 is a conceptual diagram illustrating a method for reusing desulfurized slag according to the present invention.
FIG. 2 is a diagram showing the frequency distribution of the difference between the actual S concentration and the target S concentration in the hot metal obtained by performing the method of reusing desulfurized slag (with recycling) and the conventional method (without recycling) according to the present invention. It is.
FIG. 3 is a graph showing a relationship between a desulfurizing agent basic unit (kg / t) excluding the amount of desulfurized slag used and a desulfurization rate (ln (S 0 / S f )).
FIG. 4 is a flowchart for explaining the content of a cold reuse experiment of desulfurized slag, which is the basis of the present invention.
FIG. 5 is a view showing an experimental result of FIG. 4;
[Explanation of symbols]
1 Hot metal pot for desulfurization slag recovery 2 Slag removal site 3 Slag pot 4 Refining vessel 5 Desulfurization slag 6 Arrow indicating the direction to the desulfurization site

Claims (2)

転炉装入前の溶銑を予め精錬容器に保持し、石灰系脱硫剤の投入と攪拌により該溶銑の脱硫を行うに際して、
前記脱硫で発生し、前記溶銑と分離して精錬容器より排出した高温のスラグを、脱硫を行う精錬容器中の溶銑へ、その脱硫剤の一部として投入することを特徴とする脱硫スラグの再利用方法。
When the hot metal before charging the converter is held in a refining vessel in advance, and the hot metal is desulfurized by charging and stirring a lime-based desulfurizing agent,
A high-temperature slag generated from the desulfurization and separated from the hot metal and discharged from a smelting vessel is supplied as a part of a desulfurizing agent to the hot metal in the smelting vessel for desulfurization. How to Use.
前記精錬容器が溶銑鍋であり、前記溶銑の攪拌は機械的に行うことを特徴とする請求項1記載の脱硫スラグの再利用方法。The method for reusing desulfurized slag according to claim 1, wherein the refining vessel is a hot metal pot, and the hot metal is stirred mechanically.
JP2002237358A 2002-08-16 2002-08-16 Reuse method of desulfurization slag Expired - Lifetime JP3960164B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2002237358A JP3960164B2 (en) 2002-08-16 2002-08-16 Reuse method of desulfurization slag

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2002237358A JP3960164B2 (en) 2002-08-16 2002-08-16 Reuse method of desulfurization slag

Publications (2)

Publication Number Publication Date
JP2004076088A true JP2004076088A (en) 2004-03-11
JP3960164B2 JP3960164B2 (en) 2007-08-15

Family

ID=32021138

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2002237358A Expired - Lifetime JP3960164B2 (en) 2002-08-16 2002-08-16 Reuse method of desulfurization slag

Country Status (1)

Country Link
JP (1) JP3960164B2 (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004244706A (en) * 2003-02-17 2004-09-02 Nippon Steel Corp Slag recycling method
JP2007262465A (en) * 2006-03-28 2007-10-11 Jfe Steel Kk Method for desulfurizing molten pig iron
JP2007262511A (en) * 2006-03-29 2007-10-11 Jfe Steel Kk Method for recycling desulfurization slag
JP2007332403A (en) * 2006-06-13 2007-12-27 Jfe Steel Kk Method for desulfurizing molten iron
JP2008138253A (en) * 2006-12-01 2008-06-19 Nippon Steel Corp Desulfurization refining agent for molten pig iron, and desulfurization method
CN106367560A (en) * 2016-08-29 2017-02-01 首钢京唐钢铁联合有限责任公司 Method for recycling desulphurization slag
CN106702088A (en) * 2016-11-22 2017-05-24 首钢京唐钢铁联合有限责任公司 Method for improving utilization rate of desulfurizer in KR desulfurization process
WO2017104538A1 (en) * 2015-12-17 2017-06-22 新日鉄住金エンジニアリング株式会社 Molten pig iron processing method and apparatus
KR20170130564A (en) 2015-04-27 2017-11-28 제이에프이 스틸 가부시키가이샤 Method for reuse of desulfurization slag
JP2019183269A (en) * 2018-03-30 2019-10-24 Jfeスチール株式会社 Treatment method of molten iron desulfurization slag
CN114959127A (en) * 2021-02-22 2022-08-30 宝山钢铁股份有限公司 Molten iron desulphurization slag and converter slag mixing modification co-processing method
CN115125349A (en) * 2022-06-29 2022-09-30 中冶华天工程技术有限公司 Direct pressure heat braising intelligent treatment method for molten iron pretreatment desulphurization slag

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004244706A (en) * 2003-02-17 2004-09-02 Nippon Steel Corp Slag recycling method
JP2007262465A (en) * 2006-03-28 2007-10-11 Jfe Steel Kk Method for desulfurizing molten pig iron
JP2007262511A (en) * 2006-03-29 2007-10-11 Jfe Steel Kk Method for recycling desulfurization slag
JP2007332403A (en) * 2006-06-13 2007-12-27 Jfe Steel Kk Method for desulfurizing molten iron
JP2008138253A (en) * 2006-12-01 2008-06-19 Nippon Steel Corp Desulfurization refining agent for molten pig iron, and desulfurization method
KR20170130564A (en) 2015-04-27 2017-11-28 제이에프이 스틸 가부시키가이샤 Method for reuse of desulfurization slag
KR20170102985A (en) * 2015-12-17 2017-09-12 신닛떼쯔 수미킨 엔지니어링 가부시끼가이샤 Charcoal treatment method and apparatus
WO2017104538A1 (en) * 2015-12-17 2017-06-22 新日鉄住金エンジニアリング株式会社 Molten pig iron processing method and apparatus
CN107406897A (en) * 2015-12-17 2017-11-28 新日铁住金工程技术株式会社 iron liquid processing method and device
KR101947302B1 (en) 2015-12-17 2019-02-12 신닛떼쯔 수미킨 엔지니어링 가부시끼가이샤 Charcoal treatment method and apparatus
CN107406897B (en) * 2015-12-17 2019-06-25 新日铁住金工程技术株式会社 Iron liquid processing method and device
CN106367560A (en) * 2016-08-29 2017-02-01 首钢京唐钢铁联合有限责任公司 Method for recycling desulphurization slag
CN106702088A (en) * 2016-11-22 2017-05-24 首钢京唐钢铁联合有限责任公司 Method for improving utilization rate of desulfurizer in KR desulfurization process
JP2019183269A (en) * 2018-03-30 2019-10-24 Jfeスチール株式会社 Treatment method of molten iron desulfurization slag
CN114959127A (en) * 2021-02-22 2022-08-30 宝山钢铁股份有限公司 Molten iron desulphurization slag and converter slag mixing modification co-processing method
CN114959127B (en) * 2021-02-22 2023-08-11 宝山钢铁股份有限公司 Molten iron desulfurization slag and converter slag mixing modification co-treatment method
CN115125349A (en) * 2022-06-29 2022-09-30 中冶华天工程技术有限公司 Direct pressure heat braising intelligent treatment method for molten iron pretreatment desulphurization slag

Also Published As

Publication number Publication date
JP3960164B2 (en) 2007-08-15

Similar Documents

Publication Publication Date Title
CA2715322C (en) Method for removing copper in steel scraps
JP5569174B2 (en) Method for recovering iron and phosphorus from steelmaking slag, blast furnace slag fine powder or blast furnace slag cement, and phosphoric acid resource raw material
CN109022644B (en) Method for recovering slag desulfurization and dephosphorization in cooperation with ferrite in full-three-removal process
JP2004076088A (en) Method for recycling desulfurization slag
JP5017935B2 (en) Hot metal desulfurization treatment method
JP5895887B2 (en) Desulfurization treatment method for molten steel
JP3293383B2 (en) How to use hot metal slag
JP4933032B2 (en) Hot metal desulfurization method
JP2006265623A (en) Method for pre-treating molten iron
JP4998677B2 (en) Reuse method of desulfurization slag
JP4609010B2 (en) Steel manufacturing method
JP4687307B2 (en) Hot metal desulfurization method
JP2002129221A (en) Method for refining molten iron
JP4254412B2 (en) Hot metal desulfurization method
JPH05156338A (en) Method for reusing low phosphorus converter slag
CN107779553A (en) Recycling method of L F furnace refining slag
JP4772454B2 (en) Hot metal refining method
JP3419254B2 (en) Hot metal dephosphorization method
JP3793390B2 (en) Hot metal desiliconization and desulfurization methods
JP4214928B2 (en) Hot metal pretreatment method
JP2000256720A (en) Method for refining molten iron
JP2005200762A (en) Method for desulfurizing molten pig iron
JP2005146333A (en) Method for utilizing desulfurization slag
JP3626668B2 (en) Hot metal desulfurization method
JP2842248B2 (en) Hot metal desulfurization method

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20050624

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20070123

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20070130

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20070330

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20070424

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20070507

R150 Certificate of patent or registration of utility model

Ref document number: 3960164

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20110525

Year of fee payment: 4

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120525

Year of fee payment: 5

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120525

Year of fee payment: 5

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20130525

Year of fee payment: 6

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20140525

Year of fee payment: 7

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

EXPY Cancellation because of completion of term