EP0530552B1 - 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
EP0530552B1
EP0530552B1 EP92113707A EP92113707A EP0530552B1 EP 0530552 B1 EP0530552 B1 EP 0530552B1 EP 92113707 A EP92113707 A EP 92113707A EP 92113707 A EP92113707 A EP 92113707A EP 0530552 B1 EP0530552 B1 EP 0530552B1
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Prior art keywords
solids
melt
gas
injected
process according
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EP92113707A
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German (de)
English (en)
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EP0530552A1 (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
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Thyssen Stahl AG
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Thyssen Stahl AG
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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 a method for treating pig iron melts for their desulphurization 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, the treatment in three phases is carried out, as well as 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, solids are blown in that form a basic, deoxizing, slag covering the pig iron melt and cause the melt to circulate.
  • the features of the two further phases correspond to those of claim 1.
  • the deoxidizing solids that are blown into the pig iron melt during phase I are selected from the group aluminum and polyethylene.
  • Polyethylene works directly in the slag area and reduces oxygen activity; overall, the absorption capacity of the initial slag for sulfides is increased.
  • the calcium compounds which are blown into the pig iron melt as a desulfurizing agent during the middle phase and the final phase are selected from the group of flowable, reactive lime and technical calcium carbide.
  • the magnesium-containing solids that are blown into the pig iron melt during the middle phase of the treatment are selected from the group consisting of metallic magnesium, with or without coatings, alone or in a mixture with lime, CaC2, calcium aluminates, alumina and magnesium oxide.
  • the fluxes which are blown into the melt in the final phase of the treatment are selected 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, metallurgical aluminum.
  • 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 make 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 generated orbital movement 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 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 iron granules content is low.
  • the fine-grained solids are removed 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. 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 as well as 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 4 there must be a separate pressure delivery vessel for each fine-grained solid, the effort for pressure delivery vessels can be restricted in the method variant according to claim 5.
  • 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 in each case 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 in a transfer pan, for example, 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 successively and the quantities per unit of 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 oxidized slag was largely removed before the start of the treatment and a basic, deoxidized slag was formed by blowing in a lime-fluorspar mixture. Flame coal was used as a stirring and deoxidizing agent.
  • the slag was largely removed before treatment.
  • cleaning was carried out with pre-melted calcium aluminate, and the stirring energy was introduced by means of a large amount of conveying gas.
  • CaC5 was injected continuously in all 3 phases.
  • 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. During phases II and III, 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.
  • 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 the CaD, the desulfurization effect deteriorates. In this case, this did not occur, as the result shows.
  • the slag was light and crumbly and contained little iron.

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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)
  • Manufacture And Refinement Of Metals (AREA)

Claims (19)

  1. Procédé de traitement métallurgique de fontes en fusion dans une cuve, en particulier dans une poche de coulée pour transvasement, comportant un laitier initial oxydé acide, par insufflation dans la masse fondue, à l'aide d'une lance de soufflage, de particules solides à grains fins, avec un gaz vecteur, le traitement étant effectué en trois phases, ledit procédé étant caractérisé en ce que
    a) dans la phase initiale, on insuffle des particules solides, qui désoxydent le laitier initial et augmentent sa basicité et qui communiquent en même temps à la masse fondue un mouvement circulaire,
    b) dans la phase intermédiaire, on insuffle un ou plusieurs agent(s) de désulfuration pour la désulfuration principale, et
    c) dans la phase finale, or, insuffle des substances solides qui purifient la masse fondue et exercent une désulfuration finale, et qui agissent sur le laitier de désulfuration formé de telle sorte que sa teneur en granules de fer soit faible.
  2. Procédé de traitement métallurgique de fontes en fusion dans une cuve, en particulier dans une poche de coulée pour transvasement, par insufflation dans la masse fondue, à l'aide d'une lance de soufflage, de particules solides à grains fins, avec un gaz vecteur, après élimination d'un laitier initial oxydé acide, le traitement étant effectué en trois phases, le procédé étant caractérisé en ce que
    a) dans la phase initiale, on insuffle des particules solides, qui forment un laitier désoxydé basique recouvrant la fonte en fusion et qui communiquent à la masse fondue un mouvement circulaire,
    b) dans la phase intermédiaire, on insuffle un ou plusieurs agent(s) de désulfuration pour la désulfuration principale, et
    c) dans la phase finale, on insuffle des substances solides qui purifient la masse fondue et exercent une désulfuration finale, et qui agissent sur le laitier de désulfuration formé de telle sorte que sa teneur en granules de fer soit faible.
  3. Procédé selon la revendication 1 ou 2, caractérise en ce que
    a) dans la phase initiale, on insuffle des substances solides désoxydantes et/ou calcaires et/ou libératrices de gaz,
    b) dans la phase intermédiaire du traitement, on insuffle, comme agents désulfurants, des solides contenant du magnésium et/ou des composés calciques, éventuellement en présence de solides libérateurs de gaz,
    c) dans la phase finale, on insuffle des composés calciques, éventuellement en présence de solides libérateurs de gaz et de fondants.
  4. Procédé selon une quelconque des revendications 1 à 3, caractérisé en ce que les solides à grains fins sont prélevés, à l'état de mélange ou séparément, à partir de réservoirs d'alimentation pressurisés séparés et sont insufflés dans la masse fondue par l'intermédiaire d'une conduite commune munie d'une lance de soufflage.
  5. Procédé selon une quelconque des revendications 1 à 3, caractérisé en ce que deux ou trois solides à grains fins sont chaque fois prélevés, à l'état de mélange ou séparément, à partir de réservoirs d'alimentation pressurisés séparés et sont insufflès dans la masse fondue par l'intermédiaire d'une conduite commune munie d'une lance de soufflage.
  6. Procédé selon une quelconque des revendications 1 à 5, caractérisé en ce qu'on règle la quantité de gaz vecteur insufflé en fonction de la quantité de solides insufflés et la quantité totale de gaz d'agitation Vg, de telle sorte que l'on ait une densité d'énergie d'agitation dissipée DEdiss dans la masse fondue d'au moins 100 W/t de fonte, d'après la relation:
    Figure imgb0023
     dans laquelle
    Vg = somme de la quantité de gaz vecteur insufflé, de la quantité de gaz libéré dans la masse fondue et de la quantité de gaz obtenu par vaporisation du magnésium métallique à partir de solides contenant du magnésium
    T₁ = température de la masse fondue, en °K
    g = accélération dite à la pesanteur, en m/s²
    ρ₁ = densité de la masse fondue, en kg/m³
    Hb = hauteur de la masse fondue, qui est parcourue par des bulles de gaz, en m
    Po = pression de la masse fondue, en bars
    P = poids de la masse fondue traitée, en t (tonnes).
  7. Procédé selon la revendication 6, caractérisé en ce que la densité d'énergie dissipée DEdiss est réglée à une valeur comprise entre 200 et 1000 W/t de fonte.
  8. Procédé selon une quelconque des revendications 1 à 7, caractérisé en ce que la densité d'énergie dissipée DEdiss est réglée, dans la phase initiale, à des valeurs comprises entre 600 et 1000 W/t de fonte, et, dans les phases intermédiaire et finale, à des valeurs comprises entre 200 et 700 W/t.
  9. Procédé selon une quelconque des revendications 3 à 9, caractérisé en ce qu'on diminue la quantité insufflée de solides contenant du magnésium, au fur et à mesure que la teneur en soufre s'abaisse, et on augmente la quantité de composés calciques insufflés ainsi que de solides libérateurs de gaz et/ou la quantité de gaz vecteur insufflé.
  10. Procédé selon une quelconque des revendications 3 à 9, caractérisé en ce, que les solides calcaires sont choisis dans le groupe formé par la chaux (CaO), le calcaire (CaCO₃) et la dolomite.
  11. Procédé selon une quelconque des revendications 3 à 10, caractérisé en ce que les solides libérateurs de gaz pour la phase initiale sont choisis dans le groupe formé par le charbon flambant, le charbon gras à longue flamme, le lignite, le calcaire et la dolomite.
  12. Procédé selon une quelconque des revendications 3 à 10, caractérisé en ce que les solides libérateurs de gaz pour les deuxième et troisième phases sont choisis parmi le charbon flambant, le charbon gras à longue flamme, le lignite et la chaux diamidée.
  13. Procédé selon une quelconque des revendications 1 à 12, caractérisé en ce que les solides désoxydants sont choisis parmi l'aluminium et le polyéthyléne.
  14. Procédé selon une quelconque des revendications 3 à 13, caractérisé en ce que les composés calciques sont choisis dans le groupe formé par la chaux vive à écoulement fluide et le carbure de calcium technique.
  15. Procédé selon une quelconque des revendications 3 à 14, caractérisé en ce que les solides contenant du magnésium sont choisis dans le groupe formé par le magnésium métallique, avec ou sans revêtement, seul ou en mélange avec de la chaux, du carbure de calcium, des aluminates de calcium, de l'alumine et de l'oxyde de magnésium.
  16. Procédé selon une quelconque des revendications 3 à 15, caractérisé en ce que les fondants sont choisis dans le groupe formé par le spath fluor et le carbonate de sodium.
  17. Procédé selon une quelconque des revendications 3 à 16, caractérisé en ce que les solides calcaires sont mélangés avec un solide contenant de l'aluminium.
  18. Procédé selon la revendication 14, caractérisé en ce que le carbure de calcium technique est mélangé avec un solide contenant de l'aluminium.
  19. Procédé selon la revendication 17 ou 18, caractérisé en ce que les solides contenant de l'aluminium sont choisis parmi l'aluminium et l'aluminium de première fusion.
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

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

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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)

Families Citing this family (14)

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Publication number Priority date Publication date Assignee Title
AT406690B (de) * 1994-12-09 2000-07-25 Donau Chemie Ag Mittel zur behandlung von roheisen- und gusseisenschmelzen zum zweck der entschwefelung
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
AT407644B (de) * 1999-06-08 2001-05-25 Voest Alpine Ind Anlagen Verfahren zur schlackenkonditionierung sowie anlage hierzu
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
DE102009030190A1 (de) 2009-06-24 2011-01-13 Lischka, Helmut, Dr. Injektionsmetallurgisches Einblasverfahren
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

Family Cites Families (6)

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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
DE3168626D1 (en) * 1981-07-27 1985-03-14 Thyssen Ag Process for lowering the iron content of slags rich in cao formed in the course of the desulphurisation of pig iron
FR2514368B1 (fr) * 1981-10-12 1987-07-31 Siderurgie Fse Inst Rech Procede de desulfuration de la fonte par le magnesium
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
DE3942405A1 (de) * 1989-12-21 1991-06-27 Krupp Polysius Ag Verfahren und foerderanlage zum einblasen von pulverfoermigem behandlungsmittel in roheisen- und stahlschmelzen

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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
EP0530552A1 (fr) 1993-03-10
CZ263892A3 (en) 1993-03-17
UA32411C2 (uk) 2000-12-15
RO115651B1 (ro) 2000-04-28
ATE118825T1 (de) 1995-03-15

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