EP0342132A1 - Verfahren zur Entschwefelung von Roheisen - Google Patents

Verfahren zur Entschwefelung von Roheisen Download PDF

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Publication number
EP0342132A1
EP0342132A1 EP89420132A EP89420132A EP0342132A1 EP 0342132 A1 EP0342132 A1 EP 0342132A1 EP 89420132 A EP89420132 A EP 89420132A EP 89420132 A EP89420132 A EP 89420132A EP 0342132 A1 EP0342132 A1 EP 0342132A1
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EP
European Patent Office
Prior art keywords
iron
composite product
wall
phase
alloyed
Prior art date
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EP89420132A
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English (en)
French (fr)
Inventor
Michel Douchy
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Affival SA
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Affival SA
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Publication date
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Publication of EP0342132A1 publication Critical patent/EP0342132A1/de
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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
    • 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
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
    • 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

Definitions

  • the process which is the subject of the invention relates to the desulfurization of cast irons and more particularly of cast irons produced in a blast furnace and intended for conversion into steel.
  • a first bag desulfurization process is described by M. BR ⁇ MMING and C.G. NILSSON (Revue de Métallurgie CIT June 1987 p: 487-497).
  • the process consists in substituting for the use of CO3Na2 whose effectiveness is insufficient, a desulfurizing mixture containing by mass: 85% of a binary mixture with 75% of C2Ca and 25% of CO3Ca and 15% of Mg in granules.
  • the desulphurizing mixture is injected into the pocket of liquid iron by means of a lance which introduces deep into the liquid iron the desulphurizing mixture fluidized by nitrogen.
  • a first desulphurization treatment is carried out by adding 1 to 1.5 kg of CO3Na2 per ton of pig iron in the ladle which receives about 200 tonnes of liquid pig iron from the blast furnace.
  • the desulphurizing action of this CO3Na2 takes place during the transfer from the ladle to the steelworks where, in a second stage, a cored wire is introduced into the liquid iron.
  • This cored wire 9 mm in outside diameter, has a steel casing 0.4 mm thick and contains a mixture consisting of 78% Mg and 22% C2Ca.
  • This process comprises a first phase during which the liquid pig iron, coming directly or indirectly from the blast furnace, is loaded in a pocket in which it is brought into contact with at least one oxide, a carbonate, a carbide of a metal of the group comprising Na, K, Mg, Ca.
  • At least one of the following compounds is chosen: CO3Na2, CO3Ca, C2Ca, CaO or MgO.
  • a renewed contact in the pocket between the liquid iron and the chosen compound (s) is favored using known means such as simultaneous introduction of the compound (s) and the iron, direct injection into the liquid iron by means of a lance in the case of compounds such as C2Ca, CaO, or MgO, Co3Na2, Co3C a , etc., or any other means known to those skilled in the art.
  • CO3Na2 is used which allows the formation of a slag particularly suitable for fixing significant amounts of sulfur.
  • the amount of CO3Na2 or of at least one other compound is preferably chosen in the field between approximately 1 and 12 Kg per ton of liquid iron and preferably 1 to 8 Kg per ton of liquid iron.
  • the pulverulent or granular material contained in the annular zone comprises at least one compound belonging to the group of compounds which can be used in the first phase of the process.
  • C2Ca, CaO, MgO are advantageously used.
  • a compound having insulating properties can also be provided such as grains of a refractory compound of low thermal conductivity.
  • the quantity of Mg introduced per ton of liquid pig iron depends on the initial sulfur content of the pig iron to be treated and is approximately 0.1 to 1 kg and the quantity of compound in the annular zone is preferably between 0.1 and 2 Kg per ton of pig iron.
  • the decantation of the sulfur is favored, most of which has been fixed in the form of solid particles of magnesium sulfide.
  • This is done by insufflating a gas, such as nitrogen or argon, through the liquid iron by means of a submerged lance up to the vicinity of the bottom of the pocket or of a porous plug. located itself near the bottom of this pocket.
  • a gas such as nitrogen or argon
  • the duration of insufflation of this gas preferably does not exceed a dozen minutes and is generally limited to a duration of 2 to 10 minutes and preferably 2 to 4 minutes.
  • a fourth phase of the process comprises a scrub which makes it possible to remove the slag rich in sulfur and thus avoiding the risks of resulfurization of the cast iron.
  • a metal or alloy is used for the outer envelope of the composite product, the melting temperature of which does not substantially exceed that of liquid iron.
  • alloyed or unalloyed aluminum can be used.
  • a metal or alloy is used whose melting temperature is not higher than that of the metal or alloy of the outer envelope.
  • At least the outer envelope is closed by any closure means which does not deteriorate the quality of the materials contained inside the envelope, preferably by stapling.
  • the intermediate wall can be closed by simple approximation or by covering or also by stapling or by any other closing means which does not deteriorate the quality of the material contained in the axial zone.
  • This teaching is applied, by deforming in hollow, after closure, at least one of the two walls, intermediate wall or external envelope which contain the pulverulent or granular material, in order to produce at least one open fold; this fold is then closed by pressure forces, oriented inwardly, to reduce the diameter of the envelope without significantly modifying its perimeter and without appreciable lengthening in the length direction. It is particularly advantageous to first compact the axial zone by the method which has just been described after closing the intermediate wall, for example by stapling, then, after positioning around this intermediate wall of the filling the annular area and closing, for example by stapling the outer casing, to carry out the final compaction by the same method.
  • the invention also relates to a composite product with a tubular metal shell of great length which allows the introduction into liquid cast iron of alloyed or unalloyed magnesium for the implementation of a process for desulfurization of this cast iron.
  • This composite product is particularly effective in implementing the method which is also the subject of the invention.
  • It comprises an axial zone surrounded by an intermediate metallic tubular wall of substantially circular section which contains, at least for the most part, a first compacted powder or granular material whose magnesium content in alloyed or unalloyed form is at least equal to 40 % by mass and an annular zone between the intermediate wall and an outer metallic tubular casing of substantially circular section, this annular zone containing a second compacted powder or granular material.
  • at least the intermediate metallic tubular wall or the outer metallic tubular casing is closed by a closure means and comprises at least one fold closed on itself.
  • the edge of the closed fold is inside the compacted mass and the edges of this fold are connected to the peripheral zone of this intermediate wall or of this outer envelope.
  • the bag is then transferred to the magnesium treatment stand.
  • the temperature of the cast iron is then on average 1250 ° C.
  • This composite product 1 comprises an axial zone 2 in which is housed granular Mg in grains for example of about 1 mm compacted.
  • the intermediate tubular wall 3 of unalloyed aluminum is approximately 0.4 mm thick and approximately 9 mm in outside diameter.
  • This intermediate wall 3 is stapled at 4 and has a closed fold 5 produced along a generator and which has made it possible to ensure the compaction of the Mg grains according to the teaching of patent application FR 86 03 295 cited above.
  • the annular zone 6 contains powdered CaC2.
  • the outer casing 7 stapled at 8 is also made of unalloyed aluminum approximately 0.4 mm thick and approximately 13 mm in outside diameter.
  • the compacting of the CaC2 powder is ensured by the two closed folds 9, 10 whose closure has been ensured by the action of pressure forces directed inwards, as in the case of the intermediate casing 3, without elongation noticeable of the envelope lengthwise and without significant variation in its perimeter.
  • the axial zone contains per meter of length 54 g of Mg and the annular zone 90 g of CaC2. This composite product is introduced at a speed of 300 m / min into the cast iron.
  • the magnesium is brought into contact with the liquid iron substantially on the vertical axis of the point of entry into the iron at a depth of the order of 2.5 to 3 meters.
  • the total quantity to be introduced is 0.4 kg of Mg per tonne of liquid pig iron, ie 80 kg of Mg. A total of 1480 m of composite product is therefore introduced.
  • the corresponding amount of CaC2 introduced is 133 Kg.
  • the introduction time is slightly less than 5 minutes.
  • An insufflation of argon or nitrogen is then carried out through a porous plug housed at the bottom of the bag or by submerged lance, so as to promote the settling of the sulfides of Mg and Ca formed.
  • the insufflation time is approximately 4 minutes with a flow rate of 500 to 600 l / min.
  • the desulphurization treatment is terminated by a scrub which makes it possible to remove the slag enriched with S so as to avoid subsequent resulfurization.
  • the analyzes carried out give the following results: S contents in thousandths% by mass initial iron content 90 (i.e. 0.090%) iron content after introduction of CO3Na2 34 (or 0.034%) iron content after introduction of Mg 11 (i.e. 0.011%) iron content after nitrogen blowing 7 (i.e. 0.007%) It can be seen that the process makes it possible to remove approximately 90% of the sulfur present initially, and to reduce the sulfur content to a value less than 10 thousandths% for a starting level of 90 thousandths%.
  • the desulphurization obtained, after application to the pig iron, directly or indirectly from the blast furnace, of phases one and two of the process described leads to initial sulfur contents varying between 40 and 110 thousandths% and quantities of Mg added varying, depending on the initial sulfur between 0.1 and 0.6 kg per tonne of liquid pig iron is 60 to 90% of the initial sulfur with an average of 77%.
  • the desulphurization obtained goes to 82 to 93% of the initial sulfur with an average of 87%.
  • the CaC2 powder present in the annular zone in the case of the figure plays both the role of desulfurizer and thermal insulator.
  • This CaC2 powder can be replaced in whole or in part by another desulfurizing compound or by a thermal insulator such as a slag in granules. In this case there may be interest in slightly increasing the amount of Mg involved.

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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)
EP89420132A 1988-04-14 1989-04-12 Verfahren zur Entschwefelung von Roheisen Withdrawn EP0342132A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8804927A FR2630131B1 (fr) 1988-04-14 1988-04-14 Procede de desulfuration des fontes
FR8804927 1988-04-14

Publications (1)

Publication Number Publication Date
EP0342132A1 true EP0342132A1 (de) 1989-11-15

Family

ID=9365300

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89420132A Withdrawn EP0342132A1 (de) 1988-04-14 1989-04-12 Verfahren zur Entschwefelung von Roheisen

Country Status (8)

Country Link
US (1) US4956010A (de)
EP (1) EP0342132A1 (de)
JP (1) JPH01309913A (de)
KR (1) KR890016187A (de)
CN (1) CN1037543A (de)
BR (1) BR8901759A (de)
FR (1) FR2630131B1 (de)
ZA (1) ZA892750B (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
FR2871477B1 (fr) 2004-06-10 2006-09-29 Affival Sa Sa Fil fourre
CN100419091C (zh) * 2006-04-14 2008-09-17 南京钢铁联合有限公司 镁棒炉外铁水脱硫方法
WO2009146573A1 (zh) * 2008-06-02 2009-12-10 鞍钢股份有限公司 用于控制钢中微量元素精确加入的复合球体及其制备方法
JP6024192B2 (ja) * 2012-05-15 2016-11-09 Ｊｆｅスチール株式会社 脱硫処理後の溶銑の復硫防止方法
CN108085459A (zh) * 2017-12-28 2018-05-29 新乡市新兴冶金材料有限公司 一种铝钙镁包芯线
US11590612B2 (en) * 2018-04-27 2023-02-28 Hobart Brothers Llc Micro-porous tubular welding wire
CN115074485B (zh) * 2022-06-29 2023-07-14 鞍钢股份有限公司 一种冶金自耗体、制备及应用方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE829802C (de) * 1950-05-31 1952-01-28 Dr Aloys Wuestefeld Verfahren zur Entschwefelung und Desoxydation von Eisen- und Metallschmelzen sowie zur Erzeugung von sphaerolithischem Gusseisen
EP0263255A1 (de) * 1986-08-11 1988-04-13 Arbed S.A. Verfahren und Mittel zum gleichzeitigen Aufheizen und Reinigen von Metallbädern

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US1588761A (en) * 1922-07-13 1926-06-15 Plaques Et Poudres A Souder So Method of making a brazing stick
US1629748A (en) * 1926-01-28 1927-05-24 Stoody Co Method of making welding rods and the resulting product
US2576698A (en) * 1948-04-14 1951-11-27 Johns Manville Metal-sheathed insulating blanket and method of manufacture
US2892007A (en) * 1956-06-15 1959-06-23 Gabriel Co Coaxial line
SE312388B (de) * 1966-02-15 1969-07-14 P Strandell
US4126446A (en) * 1972-03-06 1978-11-21 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Packages for the storage of air and moisture sensitive metallurgical additives and the use of such packages
US3915693A (en) * 1972-06-21 1975-10-28 Robert T C Rasmussen Process, structure and composition relating to master alloys in wire or rod form
JPS49124281A (de) * 1973-03-09 1974-11-28
US4137446A (en) * 1974-05-22 1979-01-30 Acieries Reunies De Burbach-Eich-Dudelange S.S.Arbed Welding wire constituted by a core of welding powder enclosed by a mantle of metal and a method of producing the welding wire
JPS5214511A (en) * 1975-07-25 1977-02-03 Hitachi Cable Ltd Process for producing a linear additive
US3998625A (en) * 1975-11-12 1976-12-21 Jones & Laughlin Steel Corporation Desulfurization method
US4220031A (en) * 1975-12-18 1980-09-02 Groko Maskin Ab Method for bending section-sheet, plate strip and like material
JPS52116714A (en) * 1976-03-26 1977-09-30 Hitachi Cable Ltd Addition agent for desulfurizing pig iron
WO1979000398A1 (en) * 1977-12-16 1979-07-12 Foseco Int Desulphurisation of ferrous metals
JPS6058283B2 (ja) * 1978-03-24 1985-12-19 東ソー株式会社 冶金用添加剤の製造法
US4174962A (en) * 1978-04-27 1979-11-20 Caterpillar Tractor Co. Filled tubular article for controlled insertion into molten metal
FR2456779A1 (fr) * 1979-05-15 1980-12-12 Sofrem Produit pour la desulfuration des fontes et aciers
FR2476542B1 (de) * 1980-02-26 1983-03-11 Vallourec
US4786322A (en) * 1986-01-27 1988-11-22 The Dow Chemical Company Magnesium and calcium composite
FR2610331A1 (fr) * 1987-02-03 1988-08-05 Affival Produit composite a enveloppe tubulaire pour le traitement des bains metalliques fondus

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE829802C (de) * 1950-05-31 1952-01-28 Dr Aloys Wuestefeld Verfahren zur Entschwefelung und Desoxydation von Eisen- und Metallschmelzen sowie zur Erzeugung von sphaerolithischem Gusseisen
EP0263255A1 (de) * 1986-08-11 1988-04-13 Arbed S.A. Verfahren und Mittel zum gleichzeitigen Aufheizen und Reinigen von Metallbädern

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FACHBERICHTE HÜTTENPRAXIS METALLWEITERVERARBEITUNG, vol. 23, no. 8, août 1985, pages 594-598, Coburg, DE; R. PIEPENBROCK et al.: "Desulfurizing pig iron with magnesium-cored wire" *
PATENT ABSTRACTS OF JAPAN, vol. 2, no. 15, 31 janvier 1978, page 3960 C 77; & JP-A-52 116 714 (HITACHI DENSEN K.K.) 30-09-1977 *

Also Published As

Publication number Publication date
JPH01309913A (ja) 1989-12-14
US4956010A (en) 1990-09-11
FR2630131B1 (fr) 1990-08-03
BR8901759A (pt) 1989-11-28
ZA892750B (en) 1990-12-28
KR890016187A (ko) 1989-11-28
FR2630131A1 (fr) 1989-10-20
CN1037543A (zh) 1989-11-29

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