EP0602540A1 - 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
EP0602540A1
EP0602540A1 EP93119836A EP93119836A EP0602540A1 EP 0602540 A1 EP0602540 A1 EP 0602540A1 EP 93119836 A EP93119836 A EP 93119836A EP 93119836 A EP93119836 A EP 93119836A EP 0602540 A1 EP0602540 A1 EP 0602540A1
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EP
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Prior art keywords
weight
agent
iron
agent according
calcium carbide
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EP93119836A
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German (de)
English (en)
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EP0602540B1 (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 use for the desulfurization, dephosphorization, desiliconization and denitrification of pig iron, cast iron, ferrochrome and ferromanganese melts.
  • Some of these diluents release a gas which is said to improve the mixing of the desulfurization agent with the melt.
  • the residue from this decomposition is - regardless of whether lime hydrate or limestone is used - lime, which is in a solid state at the temperatures of the treated melts. Since diffusion processes control desulfurization with solid phases and the time available is decisive for this, the lime particles present in the solid state can hardly or only to a small extent take part in the desulfurization, which is why they are referred to as metallurgically passive.
  • DE-OS 30 08 950 proposals are described to improve the efficiency of the desulfurization agent and at the same time to master the slag problem. However, these proposals were all unsuited to solving the problems that the segregation of the components caused by different surface properties and their handling made easier.
  • part of the calcium carbide is used for chemical reactions with the carbon dioxide of the added carbonate or the water from the hydroxides.
  • hydrogen or nitrogen-releasing substances are added to the treatment agents.
  • the addition of such substances can, if hydrogen gas is formed, have a deoxidizing effect, provided that this effect is not restricted by large amounts of conveying gas. The problem of the solid reaction is not solved by these additives.
  • fluorspar as a diluting component in order to promote the liquefaction of the slag.
  • fluorspar Apart from the ecological problems with the storage of slag containing fluorspar, no fundamental desulfurizing effect can be attributed to fluorspar.
  • This crust formation is a direct consequence of the solid-liquid reaction, which has the consequence that iron granules are retained and that any slag that may be thin before the treatment begins to stiffen more and more as the process progresses.
  • the content of iron granules in such slags can be up to 70% by weight.
  • blowing technique and also the stirrer technique are disadvantageous when using calcium carbide as a desulfurizing agent due to the phenomenon of the incubation time, because during a period of about 20 to 30% of the total treatment time there is no significant reaction in the melt. until the slag on the melt has been reheated by the stirring and blowing movement and at least partially liquefied. This also applies to the case when additional slag is added, since this too must first be put in a position to take up the reaction products.
  • the invention is therefore based on the object to find a means for desulfurization, dephosphorization, desiliconization and denitrification of pig iron and cast iron melts, which is able to preserve the advantages of calcium carbide or lime and is also capable of the negative influences by suitable additives to eliminate or at least reduce the solid-liquid reaction and the constantly fluctuating operating conditions.
  • the agent should also be suitable to have a desulfurizing or dephosphorizing effect in ferrochrome and ferromanganese melts.
  • the mineral raw materials mentioned are characterized by the following features which are essential for the overall reaction: they are essentially liquid at the temperatures of the pig iron, the cast iron or the chromium and manganese melts; they depart in the course of Heating up to the temperature of the surrounding melt from gaseous phases, which greatly promote mixing. For example, the alkali-containing plagioclase and orthoclase release sodium and potassium in the melt, which evaporate.
  • the mineral raw materials mentioned or their constituents sodium and potassium lead to an improvement in the absorption capacity of the slag for sulfur, so that the distribution factor slag / melt is positively influenced. In addition, they are able to bind the unwanted steel elements sulfur and phosphorus.
  • Montmorillonites e.g. in the form of the well-known pearlite, briefly form a foam phase as soon as they get into the molten metal.
  • sodium bentonite leads to an improvement in desulfurization due to the elimination of sodium.
  • 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 by fusing 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 Na2O content to about 30% by weight.
  • the calcium carbide and / or lime content is 10 to 90% by weight, a calcium carbide content, in particular 30 to 60% by weight, is preferred.
  • the calcium carbide can be in eutectic composition (About 67 wt .-% CaC2) or be used as technical carbide (78 to 81 wt .-% CaC2, balance CaO, SiO2 and Al2O3).
  • 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, chromium or manganese ore, optionally supplemented by lime and / or an alumina carrier such as e.g.
  • Kaolinite [Al (OH) 4] 2 [Si2O5]
  • muscovite [K Al2 (OH) 2] [Si3O10]
  • montmorillonite [Al2 (OH) 2] [Si4O10]
  • the iron oxide content is particularly preferably 5 to 50% by weight, an iron oxide content of 30 to 40% by weight having been found to be the most suitable.
  • the agent according to the invention consists of 5 to 50% by weight of at least one of the raw materials zeolite, bentonite, vermiculite, and / or muscovite, the rest calcium carbide and / or lime. A proportion of these mineral raw materials in the amount of 10 to 30% by weight in the agent according to the invention is very particularly preferred.
  • the constituents of the agent according to the invention have essentially the same grain size ⁇ 9 mm, a grain size of ⁇ 0.5 mm being provided for the blowing-in process and a grain size of ⁇ 2 mm for the stirrer process.
  • the grain size of the agent is in the range of ⁇ 5 mm.
  • the agent according to the invention is either introduced into the melt via an immersion lance or applied using suitable devices.
  • the components of the agent can be combined in the lance or mixed during the task.
  • the constituents of the agent are metered separately and conveyed into the melt.
  • a series of melts of approx. 50 t each was also treated in a shaking pan with a mixture of 65% by weight calcium carbide, 25% by weight albite and 10% by weight vermiculite.
  • the desulfurization showed a very low scatter band and was improved by 15 to 25% compared to calcium carbide without additives.
  • the iron granule content was lower than with conventional use of calcium carbide.
  • the total amount of feed gas per kg of desulfurization agent in the mixtures 1 to 5 according to the invention could be kept at 6-10 Nl / kg.
  • the desulfurization rate (kg / min) could be varied between 50 and 100 kg / min for all mixtures.
  • the slag was so mobile after the treatment that it could be run off by simply tipping it over; the remaining slag could easily be removed mechanically. No crusts were observed; the favorable slag consistency was maintained over a period of time sufficient for the operational process.
  • the agent according to the invention triggered a marked dephosphorization, denitrification and desiliconization of the iron melt in parallel with the desulfurization.
  • the calm reaction of feldspar which was increased in the sintering or melt flow in the Na2O or K2O content to 30 to 50% by weight, 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, with a higher progressive effect at higher albite contents can be observed. 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.
  • the slow release of the alkali components does not lead to erupting gas bubbles, as when using soda.
  • This gradual release of the alkali constituents in the agent according to the invention prevents the other components, if any, from not being thrown out of the melt, so that a longer period of action is achieved overall.

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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)
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
DE4242328A DE4242328C2 (de) 1992-12-15 1992-12-15 Mittel zur Entschwefelung, Entphosphorung, Entsilicierung und Entstickung von Roheisen- und Gußeisenschmelzen
DE4242328 1992-12-15

Publications (2)

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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0745143B2 (fr) † 1994-12-09 2002-09-25 Donau Chemie Aktiengesellschaft Agent et application de traitement de fontes de premiere ou de deuxieme fusion de fer a des fins de desulfuration
EP1498499A1 (fr) * 2003-07-14 2005-01-19 Donau Chemie Aktiengesellschaft Agent de désulfuration de fontes metaux
CN103864472A (zh) * 2014-02-26 2014-06-18 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

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Publication number Priority date Publication date Assignee Title
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
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
BR112013023995A2 (pt) 2011-03-31 2016-12-13 Nippon Steel & Sumitomo Metal Corp fundente ambientalmente favorável para dessulfuração de aço fundido
KR101230580B1 (ko) * 2012-11-01 2013-02-06 신희찬 제강 플럭스용 바인더 조성물 및 그 제조방법
JP6640790B2 (ja) * 2017-06-22 2020-02-05 みかど化工株式会社 農業用フィルム
JP6952364B2 (ja) * 2017-06-22 2021-10-20 みかど化工株式会社 農業用フィルム
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
CN116837173B (zh) * 2023-07-11 2025-09-02 中冶京诚工程技术有限公司 一种电弧炉直接还原铁少渣冶炼过程氮含量的控制方法
CN120437954B (zh) * 2025-07-11 2025-09-19 浙江绿色智行科创有限公司 钙基吸附剂及其制备方法和应用
CN121204438B (zh) * 2025-11-25 2026-02-24 湘西自治州丰达合金科技有限公司 一种高纯高性能金属锰锭的生产制备方法

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US1890485A (en) * 1929-11-06 1932-12-13 Paul R Caruthers Method of treating metal
DE1758250B1 (de) * 1968-04-29 1971-10-28 Sueddeutsche Kalkstickstoff Mittel zum Entschwefeln von Eisenschmelzen
DE1758250C (de) * 1972-05-31 Süddeutsche Kalkstickstoff-Werke AG, 8223 Trostberg Mittel zum Entschwefeln von Eisenschmelzen
DE2252795A1 (de) * 1972-10-27 1974-05-22 Sueddeutsche Kalkstickstoff Entschwefelungsmittel fuer metallschmelzen mit wasserabspaltendem zusatz
JPS5154016A (ja) * 1974-11-07 1976-05-12 Denki Kagaku Kogyo Kk Yosennodatsuryuzai
DE2252796B2 (de) * 1972-10-27 1977-02-03 Süddeutsche Kalkstickstoff-Werke AG, 8223 Trostberg Mittel zum entschwefeln von eisenschmelzen
DE2507379B2 (de) * 1974-02-27 1978-02-23 Aikoh Co, Ltd, Tokio Entschwefelungsmittel fuer eisenschmelzen
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SU969746A1 (ru) * 1981-01-05 1982-10-30 Днепропетровский Ордена Трудового Красного Знамени Металлургический Институт Шлакообразующа смесь дл выплавки стали
EP0225560A1 (fr) * 1985-12-03 1987-06-16 Giovanni Crespi Fondant pour laitier basique utilisable dans des fours de fabrication d'aciers
EP0226994A1 (fr) * 1985-12-17 1987-07-01 SKW Trostberg Aktiengesellschaft Agent de désulfuration d'une fonte liquide ainsi que procédé de fabrication
EP0355526A2 (fr) * 1988-08-23 1990-02-28 Giovanni Crespi Agent de désulfuration pour laitiers basiques d'acier et procédé pour sa fabrication
SU1713936A1 (ru) * 1989-07-26 1992-02-23 Карагандинский металлургический комбинат Способ передела фосфористого чугуна в конвертере

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DE2252795A1 (de) * 1972-10-27 1974-05-22 Sueddeutsche Kalkstickstoff Entschwefelungsmittel fuer metallschmelzen mit wasserabspaltendem zusatz
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EP0225560A1 (fr) * 1985-12-03 1987-06-16 Giovanni Crespi Fondant pour laitier basique utilisable dans des fours de fabrication d'aciers
EP0226994A1 (fr) * 1985-12-17 1987-07-01 SKW Trostberg Aktiengesellschaft Agent de désulfuration d'une fonte liquide ainsi que procédé de fabrication
EP0355526A2 (fr) * 1988-08-23 1990-02-28 Giovanni Crespi Agent de désulfuration pour laitiers basiques d'acier et procédé pour sa fabrication
SU1713936A1 (ru) * 1989-07-26 1992-02-23 Карагандинский металлургический комбинат Способ передела фосфористого чугуна в конвертере

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0745143B2 (fr) † 1994-12-09 2002-09-25 Donau Chemie Aktiengesellschaft Agent et application de traitement de fontes de premiere ou de deuxieme fusion de fer a des fins de desulfuration
EP1498499A1 (fr) * 2003-07-14 2005-01-19 Donau Chemie Aktiengesellschaft Agent de désulfuration de fontes metaux
CN103864472A (zh) * 2014-02-26 2014-06-18 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
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

Also Published As

Publication number Publication date
ZA939420B (en) 1994-08-10
US5385599A (en) 1995-01-31
DE4242328A1 (de) 1994-06-16
JPH06235011A (ja) 1994-08-23
ATE214106T1 (de) 2002-03-15
DE59310267D1 (de) 2002-04-11
DE4242328C2 (de) 1995-06-08
EP0602540B1 (fr) 2002-03-06

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