EP0164592B1 - Agent de désulfuration à grain fin pour des bains de fonte brute et procédé de désulfuration - Google Patents

Agent de désulfuration à grain fin pour des bains de fonte brute et procédé de désulfuration Download PDF

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Publication number
EP0164592B1
EP0164592B1 EP85105870A EP85105870A EP0164592B1 EP 0164592 B1 EP0164592 B1 EP 0164592B1 EP 85105870 A EP85105870 A EP 85105870A EP 85105870 A EP85105870 A EP 85105870A EP 0164592 B1 EP0164592 B1 EP 0164592B1
Authority
EP
European Patent Office
Prior art keywords
component
hydrogen
agent
agent according
splitting
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.)
Expired
Application number
EP85105870A
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German (de)
English (en)
Other versions
EP0164592A1 (fr
EP0164592B2 (fr
Inventor
Heinrich Dr. Rellermeyer
Walter Meichsner
Werner Dr. Gmöhling
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.)
Skw Stahl-Technik thyssen Stahl AG GmbH
Original Assignee
SKW Trostberg AG
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6235932&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0164592(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by SKW Trostberg AG, Thyssen Stahl AG filed Critical SKW Trostberg AG
Priority to AT85105870T priority Critical patent/ATE35153T1/de
Publication of EP0164592A1 publication Critical patent/EP0164592A1/fr
Publication of EP0164592B1 publication Critical patent/EP0164592B1/fr
Application granted granted Critical
Publication of EP0164592B2 publication Critical patent/EP0164592B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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 means and methods for the desulfurization of pig iron melts.
  • Desulphurization of pig iron outside the blast furnace is an essential necessity due to the increasing sulfur content in the ores and black matter. Numerous means and processes have already been known for this, with which sufficient degrees of desulfurization can be achieved. Mixtures based on calcium carbide with diamide lime (DE-PS 17 58 250) and with additives which split off hydrogen (DE-PS 22 52 796) or water (DE-PS 22 52 795) are preferably used. Calcium-containing compounds in combination with hydrocarbons such as oil or paraffin (FR-PS 11 66 389 and US-PS 28 63 755) have already been proposed.
  • the purpose of the gas-releasing component is to distribute the finely ground particles of the basic desulfurization agent in the molten iron.
  • DE-OS 28 35 872 describes a process for the desulfurization of pig iron using a desulfurization (mixture of calcium carbide, a gas-releasing component and fluorspar; a large number of water-releasing compounds, hydrogen-releasing compounds and carbon dioxide-releasing compounds are used as gas-releasing components
  • the desulfurization agent may also contain reducing metals and metal carbides, such as aluminum, magnesium, alloys, such as calcium silicon or metal carbides.
  • Another subject is a desulfurization process, in which the desulfurization agent according to the invention is used, according to claim 13.
  • a commercially available product with contents of 70 to 85% CaC 2 is normally used as calcium carbide, but so-called eutectic carbide with contents of 65% CaC 2 and below can also be used.
  • Solid or liquid hydrocarbons can be used as the hydrogen-releasing compounds.
  • solid hydrocarbons at room temperature are, for. B. polyethylene, polypropylene, polyvinyl chloride or polystyrene.
  • liquid hydrocarbons which may contain halogen, z. B. those with boiling points between 50 and 350 ° C can be used.
  • These liquid substances are preferably used in a form absorbed in porous organic or inorganic material, which can contain up to a multiple of its own weight of hydrocarbon.
  • Preferred porous materials for this purpose are those which themselves can also split off hydrogen or have a favorable influence on the formation of slags, such as, for example, B. polyurethane foam, peat or expanded minerals.
  • Those hydrocarbons or mixtures thereof which contain little or no oxygen are preferred.
  • component A can also have 1 to 10% by weight of other constituents which have a favorable effect on the properties of the slag, such as, for example, B. fluorspar, alumina, cryolite or colemanite.
  • additives which release carbon dioxide such as, in particular, calcium carbonate, dolomite or diamide lime, individually or as a mixture, can preferably also be mixed in with component A.
  • carbon dioxide such as, in particular, calcium carbonate, dolomite or diamide lime, individually or as a mixture
  • component A additives which release carbon dioxide
  • component A can be so limited that the volume of carbon dioxide developed therefrom and any other C0 2- delivering substances present is less than the volume of hydrogen developed from the compounds which release hydrogen.
  • These substances that release carbon dioxide can be ground together with the calcium carbide. If the specified quantity conditions are adhered to, they cause practically no oxidation of the magnesium or calcium carbide in the molten iron, but increase the beneficial effect of the split off hydrogen by the CO 2 formed (which is also formed in certain quantities by the hydrocarbon).
  • component A may be expedient to additionally mix component A with brown or gas coal, anthracite or hard coal, which also have a gas-releasing effect.
  • component A can also be added in small amounts (about 0.01 to 0.5% by weight) with commercially available flow improvers such as graphite, long-chain organic amines, alcohols, esters or silicones.
  • the constituents of component A are ground and mixed intensively, the mixing process advantageously being carried out in a mill, which is preferably a tube mill, under an inert gas blanket.
  • the constituents are preferably comminuted to such an extent that 90% of the mixture have a grain size ⁇ 90 11 m and about 50% have a grain size ⁇ 50 11 m. Certain deviations from this are irrelevant to the desulfurization effect.
  • the magnesium can be added to component A in powder form in the mill or afterwards if component A is, for. B. contains a ratio of 70 to 99 wt .-% calcium carbide and 1 to 30 wt .-% essentially hydrogen-releasing compounds.
  • Components A and B can be mixed before being blown into the molten iron, so that they are conveyed pneumatically into the melt as a mixture.
  • component A can be stored separately from the magnesium after its production and to combine it with the magnesium only in the delivery line or in the lance and to introduce it together into the melt.
  • the process according to the invention is characterized in that a mixture of calcium carbide and a hydrogen-releasing compound as component A is blown into the pig iron together with component B, the magnesium.
  • components A and B in a ratio of 40 to 95 to 5 to 60% by weight.
  • 50 to 85% by weight of component A and 15 to 50% by weight of powdered magnesium are preferably blown into the molten iron at the same time.
  • Particular preference is given to 65 to 85% by weight of component A, which optionally contains the same amounts of carbon dioxide-releasing substance such as alkaline earth metal carbonate, dolomite or diamide lime and hydrogen-releasing substance such as hydrocarbon, and optionally up to 5% by weight of fluorspar and small amounts ( up to 0.5% by weight) of a flow improver, together with 15 to 35% by weight of powdered magnesium, are simultaneously blown into the pig iron melt.
  • carbon dioxide-releasing substance such as alkaline earth metal carbonate, dolomite or diamide lime and hydrogen-releasing substance such as hydrocarbon
  • the process is advantageously carried out in such a way that a blowing rate of 10 to 100 kg, preferably 15 to 80 kg, per minute of desulfurizing agent, consisting of component A and magnesium, is blown into the iron melt.
  • a blowing rate of 10 to 100 kg, preferably 15 to 80 kg, per minute of desulfurizing agent, consisting of component A and magnesium is blown into the iron melt.
  • the desulfurizing agent is preferably blown pneumatically into the molten iron as deeply as possible using a submersible lance.
  • Inert gases such as argon or nitrogen alone or as a mixture, or reactive gases which split off hydrogen and / or contain CO 2 , alone or as a mixture, are suitable as carrier gases.
  • the desulfurization agent according to the invention is suitable in connection with the blowing process described just as well for hot metal desulfurization in the transfer pan as in the transport pan (torpedo pan).
  • the particularly low requirement for injection gas has a particularly advantageous effect; the composition of the agent guarantees sufficient distribution so that a high degree of utilization of the desulfurizing agent is achieved.
  • the desulfurization agent according to the invention has considerable advantages over the known agents in connection with the method according to the invention. According to the invention, a significant increase in the degree of desulfurization is achieved or a noticeably reduced amount of desulfurizing agent is required to achieve the same desulfurization effect.
  • the compounds which cause the desulfurization of the molten iron, that is to say the calcium carbide and the magnesium, in combination with the compounds which essentially release hydrogen, are completely available for the desulfurization reaction since they are not consumed by oxidation processes.
  • Table 1 below describes various desulfurizing agents, their use and the results achieved with them. The results are averages from at least 3 desulfurization treatments each.
  • Examples 1 to 4 are comparative examples which were carried out using known desulfurization agents based on calcium carbide and diamide lime or calcium hydroxide and carbon.

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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)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Compounds Of Iron (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Claims (18)

1. Agent de désulfuration à grain fin pour bain de fonte à base de carbure de calcium et d'autres composés, constitué d'une combinaison
A) de carbure de calcium et d'au moins une substance solide ou liquide, répartie de manière homogène parmi les autres constituants du mélange, libérant de l'hydrogène à la température du bain de fonte et le cas échéant d'une substance libérant du gaz carbonique à la température du bain de fonte, le composant A pouvant contenir le cas échéant jusqu'à 0,5 % en poids d'un agent améliorant l'écoulement, ainsi que
B) de magnésium.
2. Agent suivant la revendication 1, caractérisé en ce qu'il contient 40 à 95 % en poids de composant A et 5 à 60 % en poids de magnésium.
3. Agent suivant les revendications 1 ou 2, caractérisé en ce qu'environ 90 % de la fraction solide du composant A présentent une granularité < 90 li et environ 50 % une granularité < 50 µ.
4. Agent suivant l'une des revendications 1 à 3, caractérisé en ce que le composant A contient 70 à 99 % en poids de carbure de calcium et 1 à 30 % en poids d'une substance libérant l'hydrogène.
5. Agent suivant l'une des revendications 1 à 4, caractérisé en ce que le composant A contient en outre 1 à 10% en poids d'additifs influent sur la consistance du laitier, tels que la fluorine, l'argile, la cryolithe et/ou la colemanite.
6. Agent suivant l'une des revendications 1 à 5, caractérisé en ce que le composant A contient en outre 0,01 à 0,5 % en poids d'un agent améliorant l'écoulement.
7. Agent suivant l'une des revendications 1 à 6, caractérisé en ce que le composé libérant de l'hydrogène du composant A est un hydrocarbure solide ou un hydrocarbure halogéné solide.
8. Agent suivant la revendication 7, caractérisé en ce que le composé libérant de l'hydrogène est le polyéthylène.
9. Agent suivant la revendication 7, caractérisé en ce que le composé libérant de l'hydrogène est le polypropylène.
10. Agent suivant l'une des revendications 1 à 6, caractérisé en ce que la substance libérant de l'hydrogène du composant A est un hydrocarbure liquide ou un hydrocarbure halogéné liquide ayant un point d'ébullition entre 50 et 350 °C, qui est présent à l'état imprégné dans une matière poreuse organique ou minérale.
11. Agent suivant l'une des revendications 1 à 10, caractérisé en ce que le composant A contient en outre une substance dégageant du gaz carbonique, en particulier du carbonate de calcium, de la dolomie ou/et du « diamide-chaux •, dans une quantité telle que le volume de gaz carbonique dégagé par celle-ci soit plus faible que le volume d'hydrogène libéré à la température du bain de fonte à partir de la substance libérant de l'hydrogène.
12. Agent suivant l'une des revendications 1 à 11, caractérisé en ce que le composant A contient en outre, comme composés libérant un gaz, du lignite, de la houille ou du charbon à gaz.
13. Procédé de désulfuration d'une fonte brute avec un agent suivant l'une des revendications 1 à 12, caractérisé en ce que l'agent est insufflé sous la surface du bain de fonte sous forme fluidisée avec un débit d'insufflation de 10 à 100 kg par minute et avec 3 à 30 litres de gaz de transport par kg d'agent de désulfuration.
14. Procédé suivant la revendication 13, caractérisé en ce que l'agent est insufflé dans la poche de transvasement avec une vitesse de transport de 15 à 80 kg par minute.
15. Procédé suivant les revendications 13 ou 14, caractérisé en ce que le gaz de transport est de l'azote.
16. Procédé suivant les revendications 13 ou 14, caractérisé en ce que le gaz de transport est de l'argon.
17. Procédé suivant l'une des revendications 13 à 16, caractérisé en ce qu'on fluidifie les constituants A et B dans des distributeurs séparés, en ce qu'on les réunit dans une canalisation de transport commune et en ce qu'on les insuffle par une lance dans le bain de fonte.
18. Procédé suivant les revendications 13 à 17, caractérisé en ce qu'on insuffle dans le bain de fonte 65 à 85 % en poids du composant A, qui contient des composés dégageant de l'hydrogène et du gaz carbonique dans une quantité telle que le volume d'hydrogène dégagé par ceux-ci soit plus important que le volume de gaz carbonique dégagé par ceux-ci, ainsi que le cas échéant jusqu'à 5 % en poids de fluorine et jusqu'à 0,5 % en poids d'un agent améliorant l'écoulement en même temps que 15 à 35 % en poids de magnésium pulvérisé.
EP85105870A 1984-05-16 1985-05-13 Agent de désulfuration à grain fin pour des bains de fonte brute et procédé de désulfuration Expired - Lifetime EP0164592B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85105870T ATE35153T1 (de) 1984-05-16 1985-05-13 Feinkoerniges entschwefelungsmittel fuer eisenschmelzen und verfahren zur entschwefelung von roheisenschmelzen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3418075 1984-05-16
DE3418075 1984-05-16

Publications (3)

Publication Number Publication Date
EP0164592A1 EP0164592A1 (fr) 1985-12-18
EP0164592B1 true EP0164592B1 (fr) 1988-06-15
EP0164592B2 EP0164592B2 (fr) 1991-08-14

Family

ID=6235932

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85105870A Expired - Lifetime EP0164592B2 (fr) 1984-05-16 1985-05-13 Agent de désulfuration à grain fin pour des bains de fonte brute et procédé de désulfuration

Country Status (11)

Country Link
US (1) US4592777A (fr)
EP (1) EP0164592B2 (fr)
AT (1) ATE35153T1 (fr)
AU (1) AU568056B2 (fr)
CA (1) CA1240842A (fr)
DE (1) DE3563360D1 (fr)
ES (1) ES8606504A1 (fr)
FI (1) FI78736C (fr)
IN (1) IN162816B (fr)
NO (1) NO165765C (fr)
ZA (1) ZA853556B (fr)

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3544563C2 (de) * 1985-12-17 1998-07-16 Sueddeutsche Kalkstickstoff Mittel zur Entschwefelung von geschmolzenem Eisen
BR8606249A (pt) * 1985-12-17 1987-09-29 Sueddeutsche Kalkstickstoff Composicao finamente granulada para a dessulfuracao de ferro fundido e processo para sua preparacao
US4820760A (en) * 1987-05-28 1989-04-11 Ferro Corporation Non plateout molding composition
DE3910776A1 (de) * 1988-05-10 1989-11-23 Fischer Ag Georg Verfahren zur behandlung von gusseisenschmelzen in einer offenen pfanne mittels reinmagnesium
DE3908071A1 (de) * 1989-03-13 1990-09-20 Hoechst Ag Mittel und verfahren zum entschwefeln von metallschmelzen
FR2679256B1 (fr) * 1991-07-18 1994-08-12 Pechiney Electrometallurgie Desulfurant pour fonte liquide a base de carbure de calcium agglomere.
ES2091429T3 (es) * 1991-04-02 1996-11-01 Pechiney Electrometallurgie Agente desulfurante para fundicion constituido por carburo de calcio y aglutinante organico.
FR2676457B1 (fr) * 1991-05-16 1993-07-23 Pechiney Electrometallurgie Desulfurant pour fonte constitue de magnesium et de carbure de calcium enrobes.
FR2688230A1 (fr) * 1992-03-05 1993-09-10 Pechiney Electrometallurgie Desulfurant pour la fonte a base de poudres ultrafines de magnesium ou de carbure de calcium agglomerees par un liant polymere.
US5358550A (en) * 1992-10-26 1994-10-25 Rossborough Manufacturing Company Desulfurization agent
DE19546235C2 (de) * 1995-12-12 1997-12-11 Sueddeutsche Kalkstickstoff Entschwefelungsmittel zur Koinjektionsbehandlung von Roheisenschmelzen
JP3577997B2 (ja) 1999-06-07 2004-10-20 Ｊｆｅスチール株式会社 溶銑の脱硫方法
US6372014B1 (en) 2000-04-10 2002-04-16 Rossborough Manufacturing Co. L.P. Magnesium injection agent for ferrous metal
US6352570B1 (en) 2000-04-10 2002-03-05 Rossborough Manufacturing Co., Lp Magnesium desulfurization agent
US6770115B2 (en) * 2002-10-18 2004-08-03 Remacor, Inc. Process for magnesium granules
US6989040B2 (en) * 2002-10-30 2006-01-24 Gerald Zebrowski Reclaimed magnesium desulfurization agent
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
US7731778B2 (en) * 2006-03-27 2010-06-08 Magnesium Technologies Corporation Scrap bale for steel making process
US20080196548A1 (en) * 2007-02-16 2008-08-21 Magnesium Technologies Corporation Desulfurization puck
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
WO2012095471A2 (fr) 2011-01-15 2012-07-19 DÖRING-FREISSMUTH, Mechthilde Agent de traitement pour métaux en fusion, procédé de production et utilisation de cet agent
DE102011008690A1 (de) * 2011-01-15 2012-07-19 Mechthilde Döring-Freißmuth Mittel zur Behandlung von Metallschmelzen und Verwendung desselben
DE102011116501C5 (de) 2011-10-20 2018-05-24 Almamet Gmbh Bitumen enthaltendes Entschwefelungsmittel

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US4159906A (en) * 1972-10-27 1979-07-03 Suddeutsche Kalkstickstoff-Werke Aktiengesellschaft Method and composition for the desulfurization of molten metals
DE2252796C3 (de) * 1972-10-27 1982-08-12 Skw Trostberg Ag, 8223 Trostberg Entschwefelungsmittel für Roheisen und Ferrolegierungsschmelzen
US3876421A (en) * 1972-11-09 1975-04-08 Nippon Steel Corp Process for desulfurization of molten pig iron
US3929464A (en) * 1973-08-31 1975-12-30 Union Carbide Corp Desulfurization of molten ferrous metals
DE2531047B2 (de) * 1975-07-11 1978-07-06 Kloeckner-Werke Ag, 4100 Duisburg Verfahren zum Entschwefeln von Roheisen
US3998625A (en) * 1975-11-12 1976-12-21 Jones & Laughlin Steel Corporation Desulfurization method
DE2641817C2 (de) * 1976-09-17 1985-02-14 Hoechst Ag, 6230 Frankfurt Pulvergemische zur Entschwefelung von Eisenschmelzen
US4137072A (en) * 1976-12-01 1979-01-30 Toyo Soda Manufacturing Co., Ltd. Additive for use in refining iron
WO1979000398A1 (fr) * 1977-12-16 1979-07-12 Foseco Int Desulfuration des metaux ferreux
DE2835872C3 (de) * 1978-08-16 1981-02-05 Skw Trostberg Ag, 8223 Trostberg Verfahren zur Verminderung der Staubund Flammenbelästigung bei der Handhabung der Schlacken nach der Roheisenentschwefelung mittels eines Entschwefelungsgemisches und Entschwefelungsgemisch
FR2473061A1 (fr) * 1980-01-07 1981-07-10 Sueddeutsche Kalkstickstoff Procede pour reduire le degagement de poussieres et de flammes lors de la manipulation des scories apres desulfuration de la fonte, et melange de desulfuration approprie
US4286984A (en) * 1980-04-03 1981-09-01 Luyckx Leon A Compositions and methods of production of alloy for treatment of liquid metals
DE3111510A1 (de) * 1981-03-24 1982-10-07 Hoechst Ag, 6000 Frankfurt Entschwefelungsgemisch und verfahren zu seiner herstellung

Also Published As

Publication number Publication date
FI78736C (fi) 1989-09-11
EP0164592A1 (fr) 1985-12-18
NO165765B (no) 1990-12-27
US4592777A (en) 1986-06-03
ES543217A0 (es) 1986-04-01
ZA853556B (en) 1985-12-24
ATE35153T1 (de) 1988-07-15
FI78736B (fi) 1989-05-31
EP0164592B2 (fr) 1991-08-14
NO851924L (no) 1985-11-18
AU568056B2 (en) 1987-12-10
FI851943A0 (fi) 1985-05-15
FI851943L (fi) 1985-11-17
ES8606504A1 (es) 1986-04-01
AU4254285A (en) 1985-11-21
DE3563360D1 (en) 1988-07-21
IN162816B (fr) 1988-07-09
CA1240842A (fr) 1988-08-23
NO165765C (no) 1991-04-10

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