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EP0530552A1 - Procédé pour le traitement de désulfuration de foute en fusion - Google Patents

Procédé pour le traitement de désulfuration de foute en fusion Download PDF

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Publication number
EP0530552A1
EP0530552A1 EP92113707A EP92113707A EP0530552A1 EP 0530552 A1 EP0530552 A1 EP 0530552A1 EP 92113707 A EP92113707 A EP 92113707A EP 92113707 A EP92113707 A EP 92113707A EP 0530552 A1 EP0530552 A1 EP 0530552A1
Authority
EP
European Patent Office
Prior art keywords
solids
melt
blown
gas
process according
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
EP92113707A
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German (de)
English (en)
Other versions
EP0530552B1 (fr
Inventor
Karl-Heinz Dipl.-Ing. Abele
Heinz Dipl.-Ing. Van Den Boom
Alfred Dr.Rer.Nat. Ender
Eckart Dipl.-Ing. Hees
Walter Dipl.-Ing. Meichsner
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.)
Thyssen Stahl AG
Original Assignee
Thyssen Stahl AG
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
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Application filed by Thyssen Stahl AG filed Critical Thyssen Stahl AG
Publication of EP0530552A1 publication Critical patent/EP0530552A1/fr
Application granted granted Critical
Publication of EP0530552B1 publication Critical patent/EP0530552B1/fr
Anticipated expiration legal-status Critical
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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

Definitions

  • the invention relates to a process for the treatment of pig iron melts for their desulfurization in a container, in particular in a transfer pan, which have an acidic, oxidized initial slag, by blowing fine-grained solids into the melt with a conveying gas via an injection lance, and a variant in which the initial slag is removed from the pig iron melt before the treatment and a new covering slag is formed.
  • Claim 2 identifies a process variant in which the acidic, oxidized initial slag is removed from the pig iron melt before the treatment.
  • this variant in the initial phase such solids are blown in, which form a basic, deoxizing, slag covering the pig iron melt and which cause the melt to circulate.
  • the features of the two further phases correspond to those of claim 1.
  • the deoxidizing solids which are blown into the pig iron melt during the first phase, are selected according to claim 14 from the group aluminum and polyethylene.
  • Polyethylene acts directly in the slag area and reduces oxygen activity; overall, the absorption capacity of the initial slags for sulfides is increased.
  • the calcium compounds which are blown into the pig iron melt as a desulfurization agent during the middle phase and the final phase are selected from the group of flowable, reactive lime and technical calcium carbide according to claim 15.
  • the magnesium carriers which are blown into the pig iron melt during the middle phase of the treatment are selected according to claim 16 from the group consisting of metallic magnesium, with or without coatings, alone or in a mixture with lime, CaC2, calcium aluminates, aluminum-containing ball mill dust, alumina and Magnesium oxide.
  • the fluxes which are blown into the melt in the final phase of the treatment are selected according to claim 17 from the group of fluorspar and soda (sodium carbonate).
  • the calcareous solids can be mixed with an aluminum-containing substance.
  • the aluminum-containing solids are selected from the group aluminum, smelting aluminum and aluminum-containing mill dust.
  • lime-containing and gas-releasing solids are preferably blown into the melt in the initial phase of the treatment in order to deoxidize the initial slag and to carry out a circulating movement of the melt.
  • calcareous solids such as lime as a base carrier
  • the melt is stirred by the gas-releasing solids together with the injected conveying gas.
  • the silicon and the iron oxide (FeO) of the melt are converted into silica (SiO2) and iron (Fe) by the orbital movement generated in the sense of deoxidation.
  • magnesium and calcium carbide are preferably blown in as the desulfurizing agent, the slag pretreated in the manner described being able to absorb the magnesium sulfides formed. Blowing in gas-releasing solids in this phase is also an advantage.
  • calcium carbide carriers and gas-releasing solids are preferably blown into the melt.
  • the gases split off, together with the conveying gas, help to flush out the magnesium sulfides suspended in the melt and to react the magnesium dissolved in the melt with sulfur. Flux may be blown in to condition the slag.
  • the desulfurization slag formed is influenced by these substances in such a way that their content of iron granules is low.
  • a large number of solids - base carriers, deoxidizing agents, desulfurizing agents, gas releasers, slag conditioners - are blown into the pig iron melt independently of one another in an optimally timed dosage.
  • the solids according to claim 4 can be blown into the melt simultaneously or in succession during the individual treatment phases and the amounts per unit of time can be adjusted according to the sulfur content.
  • the fine-grained solids are removed individually from separate pressure delivery vessels and blown into the melt via a common delivery line followed by a blowing lance. In this way an optimal dosage of the individual solids can be achieved.
  • two or three fine-grained solids can also be taken as a mixture and individual solids from separate pressure delivery vessels and blown into the melt via a common delivery line followed by a blowing lance. While in the process variant according to claim 5 there must be a separate pressure delivery vessel for each fine-grained solid, in the method variant according to claim 6 the effort for pressure delivery vessels can be restricted.
  • the problems associated with the known desulfurization processes described at the outset can be overcome and that an improved desulfurization effect can be achieved due to the three-phase treatment according to the invention.
  • the metallurgical process control can be adapted using process engineering means using desulfurization components that are matched to the process stages. Further advantages can be seen in the fact that a considerable reduction in the consumption of expensive desulfurizing agents is achieved with corresponding economic benefits.
  • the utilization of these agents is optimized not only by avoiding oxidation and re-sulfurization, but also by setting the most favorable conditions by controlling the kinetically important parameters, namely turbulence and the availability of the desulfurizing agent per unit of time.
  • the significantly lower consumption of desulfurizing agents has a positive and cost-effective impact, both overall and indirectly, in conjunction with low iron losses, lower amounts of slag, short treatment times and lower heat losses.
  • the pig iron melt which is located, for example, in a decanting pan, is stirred vigorously with the gas split off from the gas coal; the slag deoxidizes through the decomposition products of the gas coal and through reaction of the silicon content of the pig iron to silica and Fe.
  • Lime (CaO) is added in a short time to increase the basicity.
  • the middle phase of the treatment when the lime is withdrawn, fine-grained magnesium and relatively little calcium carbide are blown into the melt; the addition of gas coal is throttled to limit turbulence in the melt. The addition of magnesium is reduced in accordance with the course of the sulfur content in the melt.
  • the blowing in of calcium carbide and coal is increased to intensify the bath movement.
  • calcium carbide is either blown in further as required or the additive is reduced; for this purpose, the melt is stirred vigorously, on the one hand by the conveying gas and on the other hand by the gas split off from the gas coal.
  • the magnesium sulfides are advantageously flushed out of the melt.
  • a flux is blown into the melt in the final phase of the treatment.
  • the five solids used - lime, gas coal, calcium carbide, magnesium and flux - are individually in separate pressure vessels, from which they are removed and blown into the melt via a common feed line with subsequent blowing lance.
  • the pressure delivery vessels have known controllable metering valves with which the solids can be blown into the melt simultaneously or in succession and the amounts per unit time can be varied, as shown in Figure 1.
  • the solids lime and gas coal, which are blown into the pig iron melt in the initial phase of the treatment, and the solids calcium carbide and gas coal, which are blown into the pig iron melt during the middle phase and the final phase, are each mixed as a mixture Pressure delivery vessel included.
  • the expenditure on apparatus for pressure-carrying vessels can be reduced by one vessel, but the targeted influencing of the pig iron melt can be carried out somewhat less optimally than with the exemplary embodiment according to Figure 1 by using two mixtures.
  • a further variant of the treatment method according to the invention is shown in the exemplary embodiment according to FIG. 3, in which the components lime, gas coal and flux are present as a mixture, furthermore the components calcium carbide and gas coal as a mixture and magnesium as a single solid in separate pressure vessels. In this way, the outlay on equipment for the pressure delivery vessels can be further reduced.
  • the acidic, oxidic slag was largely removed beforehand and 200 kg of fine lime, packed in sacks, were added. The lance was then retracted and stirred with 1800 Nl / min argon for 2.5 minutes.
  • fine lime was blown in, first salt-coated magnesium was added, then fluorspar, with the amount of gas being increased again in this phase to intensify the stirring effects.
  • the Mg output was reduced linearly, the lime rate kept constant.
  • ball mill dust was continuously blown in in all 3 phases for deoxidation, as a by-product and for slag conditioning. Limestone (phase I) and salt-coated magnesium (phase II) were switched on. In phase III, increased gas throughput was used.
  • CaD 7525 (75% technical calcium carbide and 25% diamide lime) was used for the desulfurization.
  • This desulfurizing agent is not as advantageous as e.g. B. CaC5 with magnesium (in co-injection), because it requires long treatment times and there is a high iron loss in the final slag, due to the larger amount of slag and its high proportion of iron granules.
  • the main goal was to reduce iron losses.
  • the beneficial effect of fluorspar in this sense is known, but when added to CaD, the desulfurization effect deteriorates. This did not happen in this case, as the result shows.
  • the slag was light and crumbly and contained little iron.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Manufacture And Refinement Of Metals (AREA)
EP92113707A 1991-08-28 1992-08-12 Procédé pour le traitement de désulfuration de foute en fusion Revoked EP0530552B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4128499A DE4128499C2 (de) 1991-08-28 1991-08-28 Verfahren zur Behandlung von Roheisenschmelzen zu deren Entschwefelung
DE4128499 1991-08-28

Publications (2)

Publication Number Publication Date
EP0530552A1 true EP0530552A1 (fr) 1993-03-10
EP0530552B1 EP0530552B1 (fr) 1995-02-22

Family

ID=6439296

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92113707A Revoked EP0530552B1 (fr) 1991-08-28 1992-08-12 Procédé pour le traitement de désulfuration de foute en fusion

Country Status (14)

Country Link
US (1) US5366539A (fr)
EP (1) EP0530552B1 (fr)
AT (1) ATE118825T1 (fr)
CA (1) CA2076743A1 (fr)
CZ (1) CZ281703B6 (fr)
DE (2) DE4128499C2 (fr)
ES (1) ES2071393T3 (fr)
HU (1) HU216171B (fr)
PL (1) PL169938B1 (fr)
RO (1) RO115651B1 (fr)
RU (1) RU2096484C1 (fr)
SK (1) SK281718B6 (fr)
UA (1) UA32411C2 (fr)
ZA (1) ZA926214B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996017963A1 (fr) * 1994-12-09 1996-06-13 Donau Chemie Aktiengesellschaft Agent de traitement de fontes de premiere ou de deuxieme fusion de fer a des fins de desulfuration
AT407644B (de) * 1999-06-08 2001-05-25 Voest Alpine Ind Anlagen Verfahren zur schlackenkonditionierung sowie anlage hierzu
EP2272991A1 (fr) 2009-07-06 2011-01-12 SKW Stahl-Metallurgie GmbH Procédé et moyen destinés au traitement de scories de désulfurisation d'acier brut
DE102009030190A1 (de) 2009-06-24 2011-01-13 Lischka, Helmut, Dr. Injektionsmetallurgisches Einblasverfahren

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19535014C2 (de) * 1995-09-21 1999-03-04 Stein Ind Anlagen Inh Christel Verfahren zum Einbringen von körnigen Feststoffen in Metallschmelzen
US5873924A (en) * 1997-04-07 1999-02-23 Reactive Metals & Alloys Corporation Desulfurizing mix and method for desulfurizing molten iron
DE19833037A1 (de) * 1998-07-22 2000-01-27 Krupp Polysius Ag Verfahren zum Entschwefeln einer Roheisenschmelze
DE19833036A1 (de) * 1998-07-22 2000-01-27 Krupp Polysius Ag Verfahren zum Entschwefeln einer Roheisenschmelze
RU2164954C1 (ru) * 1999-10-22 2001-04-10 Магнитогорский государственный технический университет им. Г.И. Носова Способ десульфурации шлака
US6372013B1 (en) 2000-05-12 2002-04-16 Marblehead Lime, Inc. Carrier material and desulfurization agent for desulfurizing iron
CN1308464C (zh) * 2000-09-14 2007-04-04 杰富意钢铁股份有限公司 精炼剂以及精炼方法
US6808550B2 (en) * 2002-02-15 2004-10-26 Nucor Corporation Model-based system for determining process parameters for the ladle refinement of steel
RU2300441C1 (ru) * 2005-09-26 2007-06-10 Юрий Апполинарьевич Караник Способ изготовления отливок из чугуна доменной плавки
US7731778B2 (en) * 2006-03-27 2010-06-08 Magnesium Technologies Corporation Scrap bale for steel making process

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3955966A (en) * 1974-03-06 1976-05-11 August Thyssen-Hutte Ag Method for dispensing a fluidizable solid from a pressure vessel
EP0070912A1 (fr) * 1981-07-27 1983-02-09 Thyssen Aktiengesellschaft vorm. August Thyssen-Hütte Procédé pour abaisser la teneur en fer des scories riches en CaO formées lors de la désulfuration de la fonte
FR2514368A1 (fr) * 1981-10-12 1983-04-15 Siderurgie Fse Inst Rech Procede de desulfuration de la fonte par le magnesium
DE3942405A1 (de) * 1989-12-21 1991-06-27 Krupp Polysius Ag Verfahren und foerderanlage zum einblasen von pulverfoermigem behandlungsmittel in roheisen- und stahlschmelzen

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR8606249A (pt) * 1985-12-17 1987-09-29 Sueddeutsche Kalkstickstoff Composicao finamente granulada para a dessulfuracao de ferro fundido e processo para sua preparacao
CA1295485C (fr) * 1988-06-06 1992-02-11 Lorne E. Murphy Desulfuration du fer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3955966A (en) * 1974-03-06 1976-05-11 August Thyssen-Hutte Ag Method for dispensing a fluidizable solid from a pressure vessel
EP0070912A1 (fr) * 1981-07-27 1983-02-09 Thyssen Aktiengesellschaft vorm. August Thyssen-Hütte Procédé pour abaisser la teneur en fer des scories riches en CaO formées lors de la désulfuration de la fonte
FR2514368A1 (fr) * 1981-10-12 1983-04-15 Siderurgie Fse Inst Rech Procede de desulfuration de la fonte par le magnesium
DE3942405A1 (de) * 1989-12-21 1991-06-27 Krupp Polysius Ag Verfahren und foerderanlage zum einblasen von pulverfoermigem behandlungsmittel in roheisen- und stahlschmelzen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
73RD STEELMAKING CONFERENCE PROCEEDINGS Bd. 73, 25. März 1990, DETROIT MEETING Seiten 351 - 355 DERUSHA JR.ET AL. 'Sequenced Iron Desulfuration by Calcium Carbide/Mg Co-Injection' *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996017963A1 (fr) * 1994-12-09 1996-06-13 Donau Chemie Aktiengesellschaft Agent de traitement de fontes de premiere ou de deuxieme fusion de fer a des fins de desulfuration
AT407644B (de) * 1999-06-08 2001-05-25 Voest Alpine Ind Anlagen Verfahren zur schlackenkonditionierung sowie anlage hierzu
DE102009030190A1 (de) 2009-06-24 2011-01-13 Lischka, Helmut, Dr. Injektionsmetallurgisches Einblasverfahren
EP2272991A1 (fr) 2009-07-06 2011-01-12 SKW Stahl-Metallurgie GmbH Procédé et moyen destinés au traitement de scories de désulfurisation d'acier brut
EP2275580A1 (fr) 2009-07-06 2011-01-19 SKW Stahl-Metallurgie GmbH Procédé et moyen destinés au traitement de scories de désulfurisation d'acier brut

Also Published As

Publication number Publication date
US5366539A (en) 1994-11-22
CA2076743A1 (fr) 1993-03-01
DE59201454D1 (de) 1995-03-30
CZ281703B6 (cs) 1996-12-11
DE4128499C2 (de) 1994-11-24
RU2096484C1 (ru) 1997-11-20
PL169938B1 (pl) 1996-09-30
HUT65147A (en) 1994-04-28
ZA926214B (en) 1993-03-01
PL295696A1 (en) 1993-04-05
ES2071393T3 (es) 1995-06-16
SK281718B6 (sk) 2001-07-10
HU216171B (hu) 1999-04-28
HU9202762D0 (en) 1992-12-28
DE4128499A1 (de) 1993-03-04
SK263892A3 (en) 1996-05-08
CZ263892A3 (en) 1993-03-17
UA32411C2 (uk) 2000-12-15
RO115651B1 (ro) 2000-04-28
ATE118825T1 (de) 1995-03-15
EP0530552B1 (fr) 1995-02-22

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