EP0360223A2 - Agent et procédé de désulfuration de bains de fer fondu et procédé pour fabriquer cet agent - Google Patents

Agent et procédé de désulfuration de bains de fer fondu et procédé pour fabriquer cet agent Download PDF

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Publication number
EP0360223A2
EP0360223A2 EP89117308A EP89117308A EP0360223A2 EP 0360223 A2 EP0360223 A2 EP 0360223A2 EP 89117308 A EP89117308 A EP 89117308A EP 89117308 A EP89117308 A EP 89117308A EP 0360223 A2 EP0360223 A2 EP 0360223A2
Authority
EP
European Patent Office
Prior art keywords
agent
magnesium
calcium carbide
desulfurization
metallic component
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
EP89117308A
Other languages
German (de)
English (en)
Other versions
EP0360223A3 (fr
EP0360223B1 (fr
Inventor
Helmut Dr. Lischka
Werner Dr. Gmöhling
Gerd Dr. Hieber
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.)
Evonik Operations GmbH
Original Assignee
SKW Trostberg 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
Application filed by SKW Trostberg AG filed Critical SKW Trostberg AG
Priority to AT89117308T priority Critical patent/ATE92539T1/de
Publication of EP0360223A2 publication Critical patent/EP0360223A2/fr
Publication of EP0360223A3 publication Critical patent/EP0360223A3/fr
Application granted granted Critical
Publication of EP0360223B1 publication Critical patent/EP0360223B1/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 an agent for the desulfurization of molten iron, a process for the production thereof and a process for the desulfurization of molten iron.
  • the agent contains calcium carbide and a metallic component.
  • the desulfurization of pig iron outside the blast furnace by means of injection metallurgical processes is a firmly established process in the production of steel.
  • two methods have proven particularly useful for reducing the sulfur content in pig iron, namely desulphurization in the torpedo pan and treatment of the pig iron in the charging pan in the steel mill. Both methods are used to desulfurize by injection metallurgy, i.e. the desulfurization mixture is blown into the pig iron melt by means of an immersion lance using an inert gas stream.
  • a disadvantage of some of these processes is the use of a mixture of substances which is not stable to mixing. Magnesium, which enables rapid and targeted desulphurization of the pig iron, can therefore not be dosed with the necessary accuracy.
  • magnesium is often used in a mixture with slag, with aluminum dross or other oxidic compounds. These agents also separate and therefore do not solve the problem.
  • Patent 4,541,867 teaches the manufacture of a carbon coated granular agent which can be used as an additive to steel baths and for desulfurization thereof.
  • the agent can consist of magnesium and calcium carbide.
  • the coating is made by mixing the components of the agent with a polymerizable oil, its thermal polymerization and its subsequent partial thermal decomposition. This manufacturing process also requires a relatively large amount of equipment and high energy input.
  • the object was therefore to provide a free-flowing, low-slag and inexpensive agent which contains calcium carbide and a metallic component which is suitable for injection for the desulfurization of pig iron melts and does not have the disadvantages mentioned.
  • This object is achieved by an agent for the desulfurization of iron, containing calcium carbide and a metallic component, calcium carbide and the metallic component being in such a form that their bulk density and their grain size are in the same range.
  • an agent for the desulfurization of molten iron which consists of two components which do not separate even when standing for a long time, during transport, during long storage in the silo or during pneumatic conveying and which can therefore be metered very well.
  • This allows the rate of injection of the metallic component to be controlled very well, which is of fundamental importance for a targeted desulfurization with the result of an optimal cost-benefit effect.
  • the agent according to the invention can be used alone for desulfurization. However, it is also suitable for co-injection in conjunction with other desulfurization agents, as described, for example, in EP 0 226 994 A1.
  • the agent according to the invention essentially consists of two components, namely calcium carbide and a metallic component.
  • the metallic component can be calcium, magnesium or alloys thereof. Magnesium metal is preferably used for the desulfurization agent.
  • the respective proportion of the two components in the mixture is not critical per se and can vary within wide limits.
  • the agent according to the invention usually contains 10 to 90% by weight of calcium carbide, preferably 20 to 80% by weight, and 90 to 10% by weight, preferably 80 to 20% by weight of metallic component.
  • the two essential components according to the invention are used in such a way that their bulk density and their grain size are in the same range.
  • the bulk density of the metallic component is adjusted to the bulk weight of calcium carbide, so the bulk density is preferably set to a range from 0.7 to 1.0 g / cm3, particularly preferably 0.8 to 0.9 g / cm3 .
  • the production of the two components with the corresponding bulk density takes place according to methods known per se.
  • the grain size of the two components is also set in the same range by appropriate grinding.
  • the grain size is preferably in the range from 0.1 to 3 mm, particularly preferably 0.3 to 1 mm.
  • the two components are mixed together, fluidized and then blown in via a lance.
  • a very homogeneous mixture can be produced that does not separate even over a long period.
  • the particles of the two components are coated.
  • An adhesive is applied to the particles for coating and then a finely divided dust.
  • the coating is 1 to 10 wt .-% based on the weight of the entire grain.
  • An oily liquid that adheres to the particles is used as the adhesive. Vegetable oils, silicone oils and / or mineral oils are suitable for this.
  • a fine-particle dust is applied. Silicate dusts or oxidic dusts, such as those produced in the aluminum industry, are suitable for the coating. Examples are finely divided silica, bentonite and / or furnace filter dust from the production of calcium silicon and / or ferro silicon and / or other ferro-alloys as well as other oxidic compounds such as calcium aluminates.
  • a typical and particularly preferred composition contains 45 wt .-% magnesium, 45 wt .-% technical calcium carbide, the content of CaC2 is usually 65 to 80 wt .-%, 0.5 wt .-% of an oil and 9.5 % By weight of a laminate.
  • the coating of the agent according to the invention is particularly advantageous. This measure produces the surfaces of the same constituents of the two components calcium carbide and metallic component. A surface of the same material, for example in the form of a coating containing silica, not only gives the agent excellent flow properties, but in particular counteracts segregation of the constituents, so that the homogeneity of the agent is fully retained during transport, handling and silo storage.
  • Highly viscous oils in particular those of vegetable origin, but also silicone oils and / or mineral oils are used as adhesion promoters.
  • Another advantage of this preferred embodiment is that the oil also binds fine fractions of carbide and magnesium and in this way makes the desulfurization agent dust-free. In addition, the sensitivity of the carbide component to moisture is reduced.
  • a layer of fine dust is applied to the adhesive layer.
  • dusts with a grain size below 10 ⁇ m are used.
  • the proportion of finely divided dust in the desulfurization agent is 2 to 10% by weight.
  • the agent according to the invention is produced by simply mixing technical calcium carbide and the metallic component in the desired grain size under an inert gas atmosphere. If coated particles are used for the agent according to the invention, then after grinding the two components to the desired particle size, the particle surface is wetted with the oil and the finely divided dust is then applied.
  • the process can be carried out batchwise in drum, trough or truncated cone mixers, as well as continuously, for example in screw mixers.
  • the agent consisting of coated particles is less flammable than finely divided magnesium
  • the mixing process is also expediently carried out under a dry inert gas atmosphere in order to exclude moisture during production, in which the magnesium and calcium carbide are free, and at the same time the risk of a dust explosion due to possible exclude existing fine-particle magnesium.
  • the agent according to the invention can be blown into the molten metal without any additives or diluents using argon or nitrogen as the carrier medium. It can also be used as a co-injection partner with other desulfurization agents. Without fear of iron ejection, the agent as such or together with another desulfurization mixture can be easily blown in at a rate of 10 to 100 kg / min, the preferred blowing rate being 20 to 40 kg / min.
  • the high blowing speed enables the blowing times to be shortened considerably and, furthermore, the filling level of the pig iron pans can be increased through the calm blowing behavior of the agent.
  • the productivity of the desulfurization process is considerably improved by using the agent according to the invention.
  • the agent In order to avoid the violent magnesium evaporation reaction in the hot pig iron melt, the agent essentially contains actively desulfurizing calcium carbide and only small amounts of inactive components.
  • the hot metal was desulfurized (RE) in a charging pan containing 230 t of iron at a temperature of 1350 ° C.
  • the mixtures used for desulfurization were blown in pneumatically by means of an immersion lance using argon.
  • Example Nos. 2 and 3 were performed with the agent of the invention CaM 45 of the preferred composition.
  • CaM 45 consists of 45% by weight of technical calcium carbide, 45% by weight of magnesium metal, 9.5% by weight of furnace filter dust from FeSi production and 0.5% by weight of silicone oil.
  • the co-injection experiments No. 4 and No. 5 were carried out with CaM 45 together with CaD C5 (95% by weight technical calcium carbide + 5% by weight flame carbon).
  • Example No. 6 illustrates the co-injection of an agent CaM 25 of the composition: 25% by weight magnesium metal, 65% by weight technical calcium carbide, 9.5% by weight furnace filter dust from the CaSi production and 0.5% by weight Silicone oil, together with CaD 45.
  • a silo with 25 - 30 t of mixture 1, 2 and 3 was in each case subjected to a total of 10 m 3 gas / minute for 10 x 3 minutes. There was a 5-minute pause between the individual loosening steps so that the mixture could settle again. The entire loosening up treatment lasted 80 minutes. The mixture was then unloaded and sampled. The discharge time lasted approx. 60 minutes for 25 t, with a 6 kg sample (10 to 12 samples) being taken every 5 minutes. The removal time for the 6 kg material was approx. 20 seconds. These 6 kg were reduced to a sufficient amount for the analysis of the magnesium content using a standardized sample divider.
  • the coated mixture (CaM 45 coated) practically does not separate, the uncoated mixture (CaM 45 uncoated) undergoes only a slight separation, the size of which has not previously been achieved.
  • a desulfurization agent according to the prior art was examined in which the grain size of the magnesium was between 0.3-1 mm and that of the calcium carbide was ⁇ 0.1 mm. The loosening of this mixture caused a clear visual effect, the magnesium and calcium carbide components separating from one another, which can be seen clearly in FIG. 2.
  • the magnesium content is initially approximately 24% by weight and ends at approximately 17% by weight.
  • FIG. 3 shows the different end sulfur values (S E values) which arise during the desulfurization treatment within a 25 t mixture delivery. It can be seen that, in accordance with the visual effect shown in FIG. 3, at the beginning of the removal of the mixture from the silo, significantly lower S E values are achieved than with the remaining amount of the mixture still present in the silo.

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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)
  • Treatment Of Steel In Its Molten State (AREA)
EP89117308A 1988-09-20 1989-09-19 Agent et procédé de désulfuration de bains de fer fondu et procédé pour fabriquer cet agent Expired - Lifetime EP0360223B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89117308T ATE92539T1 (de) 1988-09-20 1989-09-19 Mittel zur entschwefelung von eisenschmelzen und ein verfahren zur herstellung des mittels sowie ein verfahren zur entschwefelung von eisenschmelzen mit dem mittel.

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3831831A DE3831831C1 (fr) 1988-09-20 1988-09-20
DE3831831 1988-09-20
IN758CA1989 IN172425B (fr) 1988-09-20 1989-09-15

Publications (3)

Publication Number Publication Date
EP0360223A2 true EP0360223A2 (fr) 1990-03-28
EP0360223A3 EP0360223A3 (fr) 1991-05-29
EP0360223B1 EP0360223B1 (fr) 1993-08-04

Family

ID=25872360

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89117308A Expired - Lifetime EP0360223B1 (fr) 1988-09-20 1989-09-19 Agent et procédé de désulfuration de bains de fer fondu et procédé pour fabriquer cet agent

Country Status (8)

Country Link
US (1) US4943317A (fr)
EP (1) EP0360223B1 (fr)
JP (1) JPH02185908A (fr)
DE (1) DE3831831C1 (fr)
ES (1) ES2044001T3 (fr)
FI (1) FI91169C (fr)
IN (1) IN172425B (fr)
PT (1) PT91761B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0511121A1 (fr) * 1991-04-02 1992-10-28 Pechiney Electrometallurgie Désulfurant pour fonte constitué de carbure de calcium et de liant organique
FR2679256A1 (fr) * 1991-07-18 1993-01-22 Pechiney Electrometallurgie Desulfurant pour fonte liquide a base de carbure de calcium agglomere.
EP0582970A1 (fr) * 1992-08-13 1994-02-16 Freissmuth, Alfred, Dr.-Ing. Produit pour désulfuration des fontes et des aciers liquides et procédé de désulfuration
WO1995033859A1 (fr) * 1994-06-08 1995-12-14 Donau Chemie Aktiengesellschaft Agent de desulfuration pour bains de fusion de fonte brute et de fonte affinee et son procede de fabrication

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4002284A1 (de) * 1989-12-04 1991-06-06 Foseco Int Mittel zum entschwefeln von eisenschmelzen
US5149364A (en) * 1990-03-14 1992-09-22 Elkem Metals Company Desulfurization agent
FR2674867B1 (fr) * 1991-04-02 1994-05-20 Pechiney Electrometallurgie Desulfurant pour fonte constitue de carbure de calcium enrobe.
FR2676457B1 (fr) * 1991-05-16 1993-07-23 Pechiney Electrometallurgie Desulfurant pour fonte constitue de magnesium et de carbure de calcium enrobes.
DE4236619C2 (de) * 1992-10-29 1996-11-28 Air Liquide Verfahren und Regenerator zum Aufheizen von Gasen
DE19546235C2 (de) * 1995-12-12 1997-12-11 Sueddeutsche Kalkstickstoff Entschwefelungsmittel zur Koinjektionsbehandlung von Roheisenschmelzen
US6352570B1 (en) 2000-04-10 2002-03-05 Rossborough Manufacturing Co., Lp Magnesium desulfurization agent
US6372014B1 (en) * 2000-04-10 2002-04-16 Rossborough Manufacturing Co. L.P. Magnesium injection agent for ferrous metal
US6989040B2 (en) * 2002-10-30 2006-01-24 Gerald Zebrowski Reclaimed magnesium desulfurization agent
US7909860B2 (en) 2003-09-03 2011-03-22 Synthes Usa, Llc Bone plate with captive clips
US7731778B2 (en) * 2006-03-27 2010-06-08 Magnesium Technologies Corporation Scrap bale for steel making process
DE102011008690A1 (de) * 2011-01-15 2012-07-19 Mechthilde Döring-Freißmuth Mittel zur Behandlung von Metallschmelzen und Verwendung desselben
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
JP5930726B2 (ja) * 2012-01-18 2016-06-08 大阪鋼灰株式会社 精錬剤
CN104531951B (zh) * 2014-12-29 2017-01-18 芜湖金龙模具锻造有限责任公司 一种铁水脱硫剂

Citations (7)

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Publication number Priority date Publication date Assignee Title
DE2422072A1 (de) * 1973-05-08 1974-12-05 Arbed Mittel zur entschwefelung von eisenschmelzen und verfahren zu seiner herstellung
DE2531047A1 (de) * 1975-07-11 1977-01-27 Kloeckner Werke Ag Verfahren zum entschwefeln von roheisen
DE2635651A1 (de) * 1975-11-14 1977-05-26 Aikoh Co Entschweflung von geschmolzenem eisen
US4541867A (en) * 1984-03-20 1985-09-17 Amax Inc. Varnish-bonded carbon-coated magnesium and aluminum granules
EP0170407A1 (fr) * 1984-06-27 1986-02-05 The BOC Group, Inc. Agents pour l'élimination d'impuretés d'un métal liquide et procédé pour leur fabrication
EP0226994A1 (fr) * 1985-12-17 1987-07-01 SKW Trostberg Aktiengesellschaft Agent de désulfuration d'une fonte liquide ainsi que procédé de fabrication
EP0292205A1 (fr) * 1987-05-22 1988-11-23 Foseco International Limited Agents de traitement métallurgique

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB964299A (en) * 1962-05-29 1964-07-22 Foseco Int Treatment of molten iron
JPS5054513A (fr) * 1973-09-14 1975-05-14
JPS5065410A (fr) * 1973-10-15 1975-06-03
US3998625A (en) * 1975-11-12 1976-12-21 Jones & Laughlin Steel Corporation Desulfurization method
DE2708424A1 (de) * 1977-02-26 1978-08-31 Sueddeutsche Kalkstickstoff Feinkoernige entschwefelungsgemische auf basis von erdalkalikarbonaten
US4094666A (en) * 1977-05-24 1978-06-13 Metal Research Corporation Method for refining molten iron and steels
DE2741588C2 (de) * 1977-09-15 1985-02-07 Skw Trostberg Ag, 8223 Trostberg Mittel zum Entschwefeln von Eisenschmelzen
DE3544562C2 (de) * 1985-12-17 1998-07-30 Sueddeutsche Kalkstickstoff Feinkörniges Mittel zur Entschwefelung von Eisenschmelzen

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2422072A1 (de) * 1973-05-08 1974-12-05 Arbed Mittel zur entschwefelung von eisenschmelzen und verfahren zu seiner herstellung
DE2531047A1 (de) * 1975-07-11 1977-01-27 Kloeckner Werke Ag Verfahren zum entschwefeln von roheisen
DE2635651A1 (de) * 1975-11-14 1977-05-26 Aikoh Co Entschweflung von geschmolzenem eisen
US4541867A (en) * 1984-03-20 1985-09-17 Amax Inc. Varnish-bonded carbon-coated magnesium and aluminum granules
EP0170407A1 (fr) * 1984-06-27 1986-02-05 The BOC Group, Inc. Agents pour l'élimination d'impuretés d'un métal liquide et procédé pour leur fabrication
EP0226994A1 (fr) * 1985-12-17 1987-07-01 SKW Trostberg Aktiengesellschaft Agent de désulfuration d'une fonte liquide ainsi que procédé de fabrication
EP0292205A1 (fr) * 1987-05-22 1988-11-23 Foseco International Limited Agents de traitement métallurgique

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
THYSSEN TECHNISCHE BERICHTE Nr. 1, 1987, Seiten 21-33, Duisburg, DE; H.P. HAASTERT et al.: "Entwicklungen der Injektionsmetallurgie bei der Stahlherstellung" *
Ullmanns Encyklopädie der technischen Chemie, 4. Auflage, Band 2, S. 302 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0511121A1 (fr) * 1991-04-02 1992-10-28 Pechiney Electrometallurgie Désulfurant pour fonte constitué de carbure de calcium et de liant organique
FR2679256A1 (fr) * 1991-07-18 1993-01-22 Pechiney Electrometallurgie Desulfurant pour fonte liquide a base de carbure de calcium agglomere.
EP0582970A1 (fr) * 1992-08-13 1994-02-16 Freissmuth, Alfred, Dr.-Ing. Produit pour désulfuration des fontes et des aciers liquides et procédé de désulfuration
WO1995033859A1 (fr) * 1994-06-08 1995-12-14 Donau Chemie Aktiengesellschaft Agent de desulfuration pour bains de fusion de fonte brute et de fonte affinee et son procede de fabrication

Also Published As

Publication number Publication date
PT91761B (pt) 1995-05-31
US4943317A (en) 1990-07-24
EP0360223A3 (fr) 1991-05-29
JPH02185908A (ja) 1990-07-20
ES2044001T3 (es) 1994-01-01
FI91169C (fi) 1994-05-25
FI894436A0 (fi) 1989-09-19
DE3831831C1 (fr) 1989-11-02
PT91761A (pt) 1990-03-30
FI91169B (fi) 1994-02-15
FI894436A (fi) 1990-03-21
JPH0438808B2 (fr) 1992-06-25
EP0360223B1 (fr) 1993-08-04
IN172425B (fr) 1993-07-24

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