EP0602540B1 - Agent pour la désulfuration, déphosphoration, désiliciation et dénitration de bains de fonte, de fonte de moulage, de ferro-chrome et de ferro-manganèse ainsi qu'un procédé - Google Patents

Agent pour la désulfuration, déphosphoration, désiliciation et dénitration de bains de fonte, de fonte de moulage, de ferro-chrome et de ferro-manganèse ainsi qu'un procédé Download PDF

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Publication number
EP0602540B1
EP0602540B1 EP93119836A EP93119836A EP0602540B1 EP 0602540 B1 EP0602540 B1 EP 0602540B1 EP 93119836 A EP93119836 A EP 93119836A EP 93119836 A EP93119836 A EP 93119836A EP 0602540 B1 EP0602540 B1 EP 0602540B1
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EP
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Prior art keywords
weight
agent
agent according
iron
melt
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Expired - Lifetime
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EP93119836A
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German (de)
English (en)
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EP0602540A1 (fr
Inventor
Alfred Dr.-Ing. Freissmuth
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    • 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

Definitions

  • the invention relates to an agent and its application for desulfurization, dephosphorization, desiliconing and denitrification of pig iron, cast iron, ferrochrome and ferromanganese melting.
  • the backlog from this Decomposition is always - whether hydrated lime or limestone is used - lime, which at the temperatures of treated melts is in the solid state.
  • lime particles present in the solid state hardly or only to a small extent on the desulfurization participate, which is why they are referred to as metallurgically passive become.
  • the known gas-releasing substances part of the calcium carbide for chemical reactions with the carbon dioxide of the added carbonate or Water from the hydroxides is consumed.
  • the treatment agents are hydrogen or nitrogen-releasing substances added. The addition such substances, if hydrogen gas is formed will have a deoxidizing effect unless this effect is restricted by large amounts of production gas. The problem the solid reaction does not experience any of these additives Solution.
  • fluorspar has no fundamental desulfurizing effect be attributed.
  • stirrer desulfurization process always the risk of crusting.
  • the slag In the field of Melt pool surface is caused by the rotation of the stirring bar the slag more or less on the wall of the Vessel pressed.
  • the calcium carbide In the forming crusts in shape the calcium carbide preferably sticks to caking, so that it is not drawn into the melt via the drum becomes. In this way, the calcium carbide burns ineffectively or remains unused in the slag. As a result Such a crust formation will damage Stirring bar and its lifespan is reduced, so that the practical use of the theoretically very effective stirring method is often restricted.
  • JP-A-51 054016 describes a desulfurization agent which consists of 70 to 99% by weight technical calcium carbide (70-80% by weight CaC 2 , the remainder essentially CaO) and 1 to 30% by weight kaolinite (main components Al 2 O 3 and SiO 2 ), montmorillonite, mica (mica) with the main components K 2 O, Al 2 O 3 and SiO 2 .
  • alkali silicates such as nepheline, syenite, orthoclase (Al 2 O 3 .6SiO 2 .K 2 O)
  • feldspar orthoclass and plagioclase
  • feldspathoid with a high content of Na 2 O and K 2 O.
  • the invention is therefore based on the object Desulphurization, dephosphorization, desilicon agents and denitrification of pig iron and cast iron melts, which has the advantages of calcium carbide or Lime is able to preserve and with suitable additives is also able to cope with the negative influences of Solid-liquid reaction and the constantly fluctuating operating conditions to eliminate or at least reduce.
  • the agent should also be suitable in ferrochrome and Ferromanganese melting desulfurizing or dephosphoric to act.
  • Independent claim 9 relates to a method for Treatment of iron, ferrochrome and ferromangan melts with the agent according to claim 1, wherein the components of the Dosed separately and conveyed into the melt become.
  • the mineral raw materials mentioned are characterized by the following and essential features for the overall reaction from: You are at the temperature of the pig iron, the Cast iron or the chrome and manganese melts essentially liquid; they depart in the course of Heating up to the temperature of the surrounding melt gaseous phases, which significantly increase the mixing favor. For example, the alkaline plagioclase and orthoclase in the melt free sodium and potassium, which evaporate.
  • the mineral mentioned Raw materials or their components lead sodium and potassium to improve the absorption capacity of the slag for sulfur, so that the distribution factor slag / Melt is positively influenced. Moreover, they can the unwanted steel elements sulfur and Bind phosphorus.
  • Montmorillonites e.g. in the form of the well-known pearlite briefly a foam phase as soon as it enters the Metal melt arrive. Leads in a comparable way Na bentonite due to the elimination of sodium for improvement desulfurization.
  • the mineral raw materials mentioned are abundant and inexpensive, are easy to process and can be used without restrictions. There are no ecological problems associated with the use of these mineral raw materials. If necessary, their composition can be optimized in their composition by sintering measures or fusion with other materials, such as sodium, lithium or potassium carbonate, among others. By adding alkali carbonate, the alkali oxide content can be increased to 50% by weight by means of a sintering or melting process. Sodium carbonate is preferably used to adjust the Na 2 O content to approximately 30% by weight.
  • the calcium carbide content is 30 to 60% by weight.
  • the calcium carbide can be in a eutectic composition (about 67% by weight CaC 2 ) or can be used as technical carbide (78 to 81% by weight CaC 2 , balance CaO, SiO 2 and Al 2 O 3 ).
  • a lime content in the agent according to the invention of 10 to 30% by weight has proven to be advantageous.
  • the agent according to the invention can be used in addition to its use as a desulfurization agent for dephosphorization, for desiliconization and for denitrification of iron melts and in ferrochrome and ferromanganese melts.
  • the agent according to the invention preferably contains at least one further additive in the form of iron oxides, iron ores, scale, chrome or manganese ore, optionally supplemented by lime and / or an alumina carrier such as kaolinite ([Al (OH) 4 ] 2 [Si 2 O 5 ]), muscovite ([K Al 2 (OH) 2 ] [Si 3 O 10 ]) or montmorillonite ([Al 2 (OH) 2 ] [Si 4 O 10 ]) in an amount of 5 to 20% by weight. -% as a slag generator.
  • the iron oxide content is particularly preferably 5 to 40% by weight, an iron oxide content of 30 to 40% by weight having been found to be the most suitable.
  • the 10 to 50 wt .-% agent according to the invention from at least one of the raw materials zeolite, bentonite, vermiculite, and / or Muskovit, remainder calcium carbide and / or lime exists.
  • the components of the agent according to the invention have essentially the same grain size ⁇ 9 mm, with a grain size of ⁇ 0.5 for the blowing process mm and a grain size of ⁇ 2 for the stirrer method mm is provided.
  • the tapping channel or tapping pan Grain of the agent in the range of ⁇ 5 mm.
  • the agent according to the invention is either a Immersion lance introduced into the melt or with suitable Devices abandoned.
  • By using two or more dosing systems can use the components of the agent combined in the lance or mixed in the task become.
  • To the composition of the agent during the To be able to change the treatment of the melt are the Components of the agent dosed separately and into the Promoted melt.
  • the tests were carried out in an open pan with approx. 185 t and in torpedo pans with approx. 220 t pig iron.
  • the initial sulfur content S A was in the range of 0.042% by weight.
  • the pig iron temperature in the tests ranged from 1350 to 1420 ° C.
  • Fig. 1 shows for the mixtures 4 and 7, which are compared to mixtures 1 to 3 by reduced Calcium carbide shares are characterized, a slightly reduced Desulphurization capacity of approx. 79% for the mixture 4 and of about 80% for the mixture 7, each with one Use of 4 kg desulfurization mixture per t melt.
  • the slag was after treatment so flexible that it can be tilted simply by tilting it could be made to expire; the rest of the slag could be easily removed mechanically. There were no crusts observed; the favorable slag consistency remained enough for an operational process received for a long time.
  • the calm reaction of feldspar which was increased to 30 to 50% by weight in the Na 2 O or K 2 O content in the sintering or melt flow, was particularly favorable and completely surprising.
  • the proportion of albite or Na 2 O-enriched albite in mixtures for targeted dephosphorization / desiliconing / denitrification was limited to approximately 15 to 50% by weight.
  • the addition to 100% was carried out with the help of scale or iron ore and lime. It was found that the nitrogen breakdown is essentially linearly related to the albite content in the mixture used, a more progressive effect being observed at higher albite contents. On the basis of these results, it is possible to reduce the nitrogen content of pig iron by 10 to 40% by weight with the addition of albite to the dephosphorization or desulfurization agent.

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  • 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)

Claims (10)

  1. Agent de désulfuration, de déphosphoration, de dé-silisation et de dénitration des bains de fusion de fer brut, de fonte brute, de ferrochrome et de ferromanganèse, composé de (total de tous les composants = 100 %-poids)
    30 à 50 %-poids de carbure de calcium technique ou de carbure de calcium autectique,
    10 à 30 %-poids d'oxyde de calcium et
    10 à 60 %-poids de l'une ou de l'autre des matières premières minérales suivantes :
    Plagioclase alcalin, par exemple feldspath-Na (albite)
    Orthoclase alcalin, par exemple feldspath potassique, néphéline, syénite à néphéline,
    Perlite,
    Bentonite,
    Vermiculite,
    Muscovite,
    Zéolithe,
    ou au choix
    5 à 40 %-poids d'oxyde de fer sous forme de minerai de fer, de calamine, de minerai de chrome ou de manganèse,
    5 à 20 %-poids d'un support d'alumine.
  2. Agent selon la revendication 1 de désulfuration, de déphosphoration, de dé-silisation et de dénitration, caractérisé en ceci qu'en plus des composants mécaniques, il y a aussi des oxydes de fer sous forme de minerai de fer ou de calamine, de minerai de chrome ou dé manganèse à raison de 5 à 40 %-poids.
  3. Agent selon les revendications 1 et 2, caractérisé en ceci que l'agent contient de l'alumine à raison de 5 à 20 %-poids.
  4. Agent selon l'une des revendications 1 ou 3, caractérisé en ceci qu'il est composé à raison de 10 à 50 %-poids d'au moins l'une des matières première minérales zéolithe, bentonite, vermiculite, muscovite, reste de carbure de calcium et d'oxyde de calcium.
  5. Agent selon la revendication 4, caractérisé en ceci qu'il est composé à raison de 10 à 30 %-poids d'au moins l'une des matières premières minérales zéolithe, bentonite, vermiculite, muscovite, reste de carbure de calcium et d'oxyde de calcium.
  6. Agent selon les revendications 1 à 5, caractérisé en ceci que les différents composants ont une granulométrie identique pour l'essentiel de ≤ 9 µm pour le procédé d'insufflation et pour l'adjonction dans la rigole de coulée ou la poche de ≤ 5 µm et pour le procédé par agitation de ≤ 2 µm.
  7. Agent selon les revendications 1 à 6, caractérisé en ceci que la teneur en oxyde alcalin est portée à une teneur jusqu'à 50 %-poids d'oxyde alcalin par frittage ou fusion des matières premières minérales.
  8. Agent selon la revendication 7, caractérisé en ceci que la teneur en oxyde de sodium des matières premières minérales est portée à une teneur de 30 %-poids d'oxyde de sodium par fonte avec la soude.
  9. Procédé de traitement du bain de fusion du fer, du ferrochrome et du ferro-manganèse avec un agent selon la revendication 1, caractérisé en ceci que l'agent est injecté par insufflation au moyen d'une lance d'immersion.
  10. Procédé de traitement des bains de fusion de fer, de ferrochrome et de ferro-manganèse avec un agent selon la revendication 1, caractérisé en ceci que les composants de l'agent sont amenés séparément, dosés et transportés dans le bain de fusion.
EP93119836A 1992-12-15 1993-12-09 Agent pour la désulfuration, déphosphoration, désiliciation et dénitration de bains de fonte, de fonte de moulage, de ferro-chrome et de ferro-manganèse ainsi qu'un procédé Expired - Lifetime EP0602540B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4242328 1992-12-15
DE4242328A DE4242328C2 (de) 1992-12-15 1992-12-15 Mittel zur Entschwefelung, Entphosphorung, Entsilicierung und Entstickung von Roheisen- und Gußeisenschmelzen

Publications (2)

Publication Number Publication Date
EP0602540A1 EP0602540A1 (fr) 1994-06-22
EP0602540B1 true EP0602540B1 (fr) 2002-03-06

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EP93119836A Expired - Lifetime EP0602540B1 (fr) 1992-12-15 1993-12-09 Agent pour la désulfuration, déphosphoration, désiliciation et dénitration de bains de fonte, de fonte de moulage, de ferro-chrome et de ferro-manganèse ainsi qu'un procédé

Country Status (6)

Country Link
US (1) US5385599A (fr)
EP (1) EP0602540B1 (fr)
JP (1) JPH06235011A (fr)
AT (1) ATE214106T1 (fr)
DE (2) DE4242328C2 (fr)
ZA (1) ZA939420B (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
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AT406690B (de) † 1994-12-09 2000-07-25 Donau Chemie Ag Mittel zur behandlung von roheisen- und gusseisenschmelzen zum zweck der entschwefelung
AT406691B (de) * 1998-06-10 2000-07-25 Holderbank Financ Glarus Verfahren zum entsilizieren von roheisen vor einem frischen zu stahl
FR2787468B1 (fr) * 1998-12-18 2001-12-07 Lorraine Laminage Procede de denitruration de l'acier en fusion en cours d'elaboration
US6143050A (en) * 1999-06-09 2000-11-07 W. R. Grace & Co.- Conn. Modifying slag for smelting steel in electric arc furnaces
AT412477B (de) * 2003-07-14 2005-03-25 Donau Chemie Ag Mittel zur entschwefelung von metallschmelzen
US20050056120A1 (en) * 2003-09-15 2005-03-17 Flores-Morales Jose Ignacio Desulphurization of ferrous materials using sodium silicate
US20050066772A1 (en) * 2003-09-26 2005-03-31 Flores-Morales Jose Ignacio Desulphurization of ferrous materials using glass cullet
CN100526480C (zh) * 2006-06-28 2009-08-12 宜兴市振球炉料有限公司 Kr法铁水预处理用脱磷剂
CN101016578B (zh) * 2007-02-14 2010-05-19 于世发 高炉熔融法生产的钢液净化渣剂
JP5413300B2 (ja) * 2010-05-07 2014-02-12 新日鐵住金株式会社 鉱物含有溶鋼脱硫フラックス
US9127327B2 (en) 2011-03-31 2015-09-08 Nippon Steel & Sumitomo Metal Corporation Environmentally friendly flux for molten steel desulfurization
KR101230580B1 (ko) * 2012-11-01 2013-02-06 신희찬 제강 플럭스용 바인더 조성물 및 그 제조방법
CN103864472B (zh) * 2014-02-26 2016-03-09 化工部长沙设计研究院 一种吸附法由钾长石分解母液制备钾肥的工艺
CN108588317B (zh) * 2018-01-25 2020-12-18 河北龙凤山铸业有限公司 一种超高纯生铁制备系统及制备方法

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Also Published As

Publication number Publication date
JPH06235011A (ja) 1994-08-23
DE4242328A1 (de) 1994-06-16
ZA939420B (en) 1994-08-10
EP0602540A1 (fr) 1994-06-22
DE59310267D1 (de) 2002-04-11
US5385599A (en) 1995-01-31
DE4242328C2 (de) 1995-06-08
ATE214106T1 (de) 2002-03-15

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