US3751242A - Process for making chrimium alloys - Google Patents

Process for making chrimium alloys Download PDF

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Publication number
US3751242A
US3751242A US00025267A US3751242DA US3751242A US 3751242 A US3751242 A US 3751242A US 00025267 A US00025267 A US 00025267A US 3751242D A US3751242D A US 3751242DA US 3751242 A US3751242 A US 3751242A
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US
United States
Prior art keywords
melt
chromium
percent
oxygen
pig iron
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 - Lifetime
Application number
US00025267A
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English (en)
Inventor
H Knuppel
K Brotzmann
H Fassbinder
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.)
Eisenwerk Sulzbach Rosenb GmbH
Eisenwerk Sulzbach Rosenberg Huette dt GmbH
Original Assignee
Eisenwerk Sulzbach Rosenb GmbH
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 Eisenwerk Sulzbach Rosenb GmbH filed Critical Eisenwerk Sulzbach Rosenb GmbH
Application granted granted Critical
Publication of US3751242A publication Critical patent/US3751242A/en
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Expired - Lifetime legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/10Handling in a vacuum
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/005Manufacture of stainless steel
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/28Manufacture of steel in the converter
    • C21C5/30Regulating or controlling the blowing
    • C21C5/34Blowing through the bath

Definitions

  • ABSTRACT A process for making a chromium alloy containing from about 10 percent to about 30 percent chromium a t ma nd ess e lyitensemp is fin n a pig iron melt containing chromium in a converter by blowing oxygen jets into the melt under the melt surface in the converter, the oxygen jets each being surrounded by a sheath of a jacket gas such as propane which is slow to react with the melt in order to protect the lining of the converter and the nozzles through which the oxygen jets are blown.
  • a jacket gas such as propane
  • the pig iron itself may contain the chromium or the chromium may be added to the melt in the form of a chromium alloy after an initial refinement of the pig iron melt in tfie conveit er and in this case further refinement by the introduction of the jacketed oxygen jets into the melt takes place after the chromium has been added. After the oxygen blowing there may be a final blow using jets of argon in place of the oxygen.
  • the invention relates to processes for making chromium alloys containing from to percent chromium, the remainder essentially iron, in which a pig iron melt containing chromium, preferably pig iron of the Stahleisen" type is refined in a converter.
  • Highly alloyed steels such as ferritic and austenitic chromium steels are usually made by melting in an electric furnace.
  • the charge consisting of scrap with a little pig iron, is oxidised to remove the phosphorus. After drawing off the slag, the sulphur is removed.
  • the alloy constituents are added in the form of ferrous alloys.
  • pig iron containing 14 to 20 percent chromium is melted in a cupola furnace, in a blast furnace or in an electric arc furnace. The melt is then refined in a converter, by means of surface blown oxygen, to produce steel.
  • the refining of melts containing chromium is preferably conducted at very high refining temperatures, that is to say at approximately l,800 C. At these temperatures the free enthalpy of chromium oxide is only a little less than the free enthalpy of ferrous oxide. The loss of chromium can be still further decreased by interrupting the refining when the carbon has been brought down to approximately 1.10 percent.
  • silicon is added to the slag. The silicon reduces part of the oxidised chromium again, increasing the chromium concentration in the melt.
  • this slag reducing process has the disadvantage that other elements, for example phosphorus, have less affinity for oxygen than silicon has, and consequently these elements are also reduced to some extent and pass back into the melt.
  • the high refining temperature used considerably accelerates destruction of the refractory converter lining, making it necessary to rebuild the converter more often.
  • very pure pig iron is preferably used for the oxygen surface blown process, the pig iron, containing for example only small quantities of phosphorus, sulphur and silicon. Due to the low concentrations of the impurities, less oxygen is required and consequently the chromium losses are reduced.
  • this advantage has to be paid for in that the process requires high quality and correspondingly costly pig iron, as the raw material.
  • the object of the present invention is to provide a process for making chromium alloys containing 10 to 30 percent chromium, the remainder essentially iron, in which chromium losses are comparatively low, in which a lower refining temperature gives the converter lining a longer working life.
  • a process for making chromium alloy containing from 10 to 30 percent chromium, the remainder essentially iron, in which a pig iron melt containing chromium, for example pig iron of the Stahleisen type, is refined in a converter the refinement is brought about by introducing at least one oxygen jet through a nozzle into the melt under the melt surface in the converter, the oxygen jet being surrounded by a sheath of a jacket gas which is slow to react with the melt in order to protect the nozzle and the lining of the conveter.
  • This invention is based on the surprising discovery that if the oxygen required for refining the pig iron is introduced into the melt from under its surface in this way considerably less chromium goes over into the slag. This low loss of chromium to the slag allows a pig iron to be used which already contains part or all of the chromium content of the alloy before the refining process begins.
  • the process thus enables the pig iron melt to be refined with little loss of chromium, at a temperature of approximately 1,700 C, the carbon being brought down to a final concentration of 0.10 percent. If it is desired to bring the carbon down still further, and to lose even less chromium to the slag, the fraction of comparatively inert jacket gas around the oxygen jet can be increased towards th end of the refining process and/or the oxygen may be mixed with an inert gas such as argon. This hardly influences the economics of the process, because the oxygen mixed with inert gas, for example argon, is blown only briefly, for example for approximately 10 percent of the total refining time.
  • inert gas such as argon
  • reaction gases may be drawn away from the melt by means of a vacuum pump so that the pressure applied to the surface of the melt is less than atmospheric, for this purpose, it is sufficient to bring the pressure above the melt down to approximately l0 percent of atmospheric.
  • the carbon can also be brought down by subjecting the melt after refinement to a vacuum treatment, in which case it is advantageous to leave all or at least part of the slag on the melt.
  • a subsequent vacuum treatment should be conducted under a more extreme vacuum than that which prevails during refining, preferably 1 percent of atmospheric pressure.
  • the process in accordance with the invention may be conducted as follows.
  • a pig iron of the usual kind is refined and then, after drawing off the slag, the necessary chromium is added in the form ofa chromium alloy, for example ferrochrome, containing approximately 6 percent of carbon and an above average concentration of silicon that is at least 3 percent silicon.
  • the high concentration of silicon in the alloy added delivers, during the oxidation, the quantity of heat necessary for melting the alloy.
  • the refining of the pig iron is preferably allowed to proceed until the melt contains only 0.05 percent carbon, 0.15 percent manganese, 0.012 percent Phorphorus and 0.014 percent sulphur.
  • EXAMPLE 1 In order to make a ferrite chromium steel containing approximately 0.10 percent carbon and 14 percent chromium, pig iron of the Stahleisen type, that is to say a pig iron containing approximately 3 to 4 percent carbon, up to 1 percent silicon, 2 to 6 percent manganese, 0.08 to 0.12 percent phosphorus and up to 0.04 percent sulphur was refined in a converter, oxygen being blown into the melt through compound nozzles installed in the converter bottom, each compound nozzle consisting of an oxygen pipe surrounded concentrically by a jacket gas pipe, to the effect that each oxygen jet was surrounded by a sheath of jacket gas which in this example was propane.
  • pig iron of the Stahleisen type that is to say a pig iron containing approximately 3 to 4 percent carbon, up to 1 percent silicon, 2 to 6 percent manganese, 0.08 to 0.12 percent phosphorus and up to 0.04 percent sulphur was refined in a converter, oxygen being blown into the melt through compound nozzles installed in the
  • the non-alloyed pig iron was initially refined to give a melt containing 0.05 percent carbon, 0.010 percent phosphorus, 0.010 percent sulphur and 0.010 percent manganese. During this refinemeent the melt temperature was 1,740 C. After drawing off the slag and reducing the melt with a 2 kg of aluminum per metric ton of steel, 23 percent of ferrochrome, based on the total weight of the finished melt, and 50 kg of lime per metric ton of steel were added to the melt. The ferrochrome consisted of 64 percent chromium, 6 percent carbon and percent silicon, the remainder iron.
  • the ferrochrome can be added in several successive portions during the second refining process. Particularly good results are obtained by blowing the lime, in the form of a fine dust, into the melt with the oxygen.
  • EXAMPLE ll Using a similar converter, a melt was refined for the purpose of making a ferrite chromium steel containing 17 percent of chromium.
  • pig iron containing 7 percent of chromium was refined.
  • This pig iron had been prepared in a 30 metric ton converter from pig iron of the Stahleisen type containing 4.2 percent carbon, 0.5 percent silicon, 0.1 percent phosphorus and 0.04 percent sulphur to which were added per metric ton of pig iron 200 kg of scrap containing 17 percent of chromium by weight and 65 kg of ferrochrome containing carbon and containing 64 percent of chromium by weight.
  • lime dust was blown with the oxygen.
  • a process for making chromium alloy containing from about 10 percent to about 30 percent chronium and the remainder essentially iron including the steps of (l) refining a pig iron melt in a convertor by introducing at least one oxygen jet into said melt through a compound nozzle located in the bottom of said convertor and discharging said oxygen jet into said melt below the surface of said melt and surrounding each said oxygen jet with a sheath of protective gas which is slow to react with the melt and which is discharged into said melt simultaneously with each said oxygen jet, in order to protect said compound nozzle and the lining of said convertor and (2) thereafter drawing slag off from said refined pig iron melt, and (3) then introducing a chromium alloy containing at least 3 percent of silicon into said pig iron melt to form a pig iron melt containing chromium (4) thereafter further refining said melt by repeating step (1) by introducing said oxygen jet into said pig iron melt containing chromium and (5) recovering the produced alloy containing 10 percent to 30 percent chromium

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Carbon Steel Or Casting Steel Manufacturing (AREA)
US00025267A 1969-04-02 1970-04-02 Process for making chrimium alloys Expired - Lifetime US3751242A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE1916945A DE1916945C3 (de) 1969-04-02 1969-04-02 Anwendung des Mantelgas-Verfahrens zum Frischen von Roheisen zu Stahl

Publications (1)

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US3751242A true US3751242A (en) 1973-08-07

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US (1) US3751242A (enrdf_load_stackoverflow)
DE (1) DE1916945C3 (enrdf_load_stackoverflow)
FR (1) FR2042874A5 (enrdf_load_stackoverflow)
GB (1) GB1271486A (enrdf_load_stackoverflow)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3891429A (en) * 1973-06-07 1975-06-24 Koppers Co Inc Method for selective decarburization of alloy steels
US3907548A (en) * 1973-07-04 1975-09-23 Krupp Ag Huettenwerke Process for the production of steels having high chromium content and lowest possible carbon content
US3909245A (en) * 1973-03-30 1975-09-30 Maximilianshuette Eisenwerk Process for lowering the iron content in nickel melts
US3929458A (en) * 1973-02-07 1975-12-30 Creusot Loire Process for the elaboration of chrome steels
US3985550A (en) * 1975-01-23 1976-10-12 United States Steel Corporation Method of producing low sulfur steel
US3990888A (en) * 1972-10-06 1976-11-09 Uddeholms Aktiebolag Decarburization of a metal melt
US3992194A (en) * 1974-04-11 1976-11-16 Creusot-Loire Method and apparatus for use in the treatment of metals in the liquid state
US4021233A (en) * 1971-10-06 1977-05-03 Uddeholms Aktiebolag Metallurgical process
US4081268A (en) * 1976-04-28 1978-03-28 Creusot-Loire Method of protecting tuyeres for upwardly blowing pure oxygen through the bottom of steel converters
US4139368A (en) * 1977-10-11 1979-02-13 Pennsylvania Engineering Corporation Metallurgical method
US4139370A (en) * 1972-01-13 1979-02-13 Gesellschaft Fur Elektrometallurgie Mbh Method of refining ferro-alloys
US4141723A (en) * 1976-09-20 1979-02-27 Institut De Recherches De La Siderurgie Francaise (Irsid) Process for producing stainless steel
US4165980A (en) * 1972-01-13 1979-08-28 Gfe Gesellschaft Fur Elektrometallurgie Mit Beschrankter Haftung Method of rapidly decarburizing ferro- alloys with oxygen
US4168158A (en) * 1977-12-08 1979-09-18 Kawasaki Steel Corporation Method for producing alloy steels having a high chromium content and an extremely low carbon content
US4174212A (en) * 1978-03-10 1979-11-13 A. Finkl & Sons Co. Method for the refining of steel
US4192675A (en) * 1978-01-17 1980-03-11 S.A. Manganese Amcor Ltd. Process for decarburizing ferro-manganese
US4330326A (en) * 1979-08-24 1982-05-18 Eisenwerk-Gesellschaft Maximilianshutte Mbh. Method and a means for introducing close-grained carbonaceous fuels into a molten iron bath
US4385753A (en) * 1980-03-05 1983-05-31 Creusot-Loire Tuyere for the simultaneous and separate introduction of at least one gas and one powder material

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2239578C3 (de) * 1971-12-20 1982-07-22 Verfahrenstechnik Dr.-Ing. Kurt Baum, 4300 Essen Gassammelhaube für Konverter
DE2243839A1 (de) * 1972-09-07 1974-03-28 Kloeckner Werke Ag Verfahren zur herstellung kohlenstoffarmer hochchromhaltiger ferritischer staehle
US4001012A (en) * 1973-11-28 1977-01-04 United States Steel Corporation Method of producing stainless steel
FR2448572B1 (fr) * 1979-02-09 1985-10-18 Pennsylvania Engineering Corp Procede d'obtention d'acier a basse teneur en carbone au convertisseur oxygene-argon
JP2850407B2 (ja) * 1989-04-18 1999-01-27 大同特殊鋼株式会社 含クロム溶鋼の精錬法

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1793153A (en) * 1927-07-20 1931-02-17 Electro Metallurg Co Process of making rustless iron alloys
US2068785A (en) * 1933-11-20 1937-01-26 United States Steel Corp Method of manufacturing low carbon steel
US2093666A (en) * 1934-11-23 1937-09-21 Wacker Chemie Gmbh Process for treating iron and iron alloys
US2562813A (en) * 1948-03-11 1951-07-31 Standard Oil Dev Co Continuous ore reducing and melting operation
US2855293A (en) * 1955-03-21 1958-10-07 Air Liquide Method and apparatus for treating molten metal with oxygen
GB882676A (en) * 1958-01-29 1961-11-15 British Oxygen Co Ltd Treatment of ferrous material
US3046107A (en) * 1960-11-18 1962-07-24 Union Carbide Corp Decarburization process for highchromium steel
GB985586A (en) * 1962-07-25 1965-03-10 British Oxygen Co Ltd Improvements in or relating to the treatment of molten steel
US3252790A (en) * 1956-06-27 1966-05-24 Union Carbide Corp Preparation of metals and alloys
FR1450718A (fr) * 1965-07-12 1966-06-24 Air Liquide Perfectionnements à des procédés métallurgiques
US3282679A (en) * 1962-09-18 1966-11-01 Gussstahlwerk Witten Ag Production of alloy steel
US3323907A (en) * 1964-11-23 1967-06-06 Air Prod & Chem Production of chromium steels
US3330645A (en) * 1962-08-07 1967-07-11 Air Liquide Method and article for the injection of fluids into hot molten metal
US3336132A (en) * 1964-03-09 1967-08-15 Crucible Steel Co America Stainless steel manufacturing process and equipment
US3468657A (en) * 1965-03-19 1969-09-23 Nyby Bruk Ab Method for refining a metal
US3594155A (en) * 1968-10-30 1971-07-20 Allegheny Ludlum Steel Method for dynamically controlling decarburization of steel

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1793153A (en) * 1927-07-20 1931-02-17 Electro Metallurg Co Process of making rustless iron alloys
US2068785A (en) * 1933-11-20 1937-01-26 United States Steel Corp Method of manufacturing low carbon steel
US2093666A (en) * 1934-11-23 1937-09-21 Wacker Chemie Gmbh Process for treating iron and iron alloys
US2562813A (en) * 1948-03-11 1951-07-31 Standard Oil Dev Co Continuous ore reducing and melting operation
US2855293A (en) * 1955-03-21 1958-10-07 Air Liquide Method and apparatus for treating molten metal with oxygen
US3252790A (en) * 1956-06-27 1966-05-24 Union Carbide Corp Preparation of metals and alloys
GB882676A (en) * 1958-01-29 1961-11-15 British Oxygen Co Ltd Treatment of ferrous material
US3046107A (en) * 1960-11-18 1962-07-24 Union Carbide Corp Decarburization process for highchromium steel
GB985586A (en) * 1962-07-25 1965-03-10 British Oxygen Co Ltd Improvements in or relating to the treatment of molten steel
US3330645A (en) * 1962-08-07 1967-07-11 Air Liquide Method and article for the injection of fluids into hot molten metal
US3282679A (en) * 1962-09-18 1966-11-01 Gussstahlwerk Witten Ag Production of alloy steel
US3336132A (en) * 1964-03-09 1967-08-15 Crucible Steel Co America Stainless steel manufacturing process and equipment
US3323907A (en) * 1964-11-23 1967-06-06 Air Prod & Chem Production of chromium steels
US3468657A (en) * 1965-03-19 1969-09-23 Nyby Bruk Ab Method for refining a metal
FR1450718A (fr) * 1965-07-12 1966-06-24 Air Liquide Perfectionnements à des procédés métallurgiques
US3594155A (en) * 1968-10-30 1971-07-20 Allegheny Ludlum Steel Method for dynamically controlling decarburization of steel

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021233A (en) * 1971-10-06 1977-05-03 Uddeholms Aktiebolag Metallurgical process
US4139370A (en) * 1972-01-13 1979-02-13 Gesellschaft Fur Elektrometallurgie Mbh Method of refining ferro-alloys
US4165980A (en) * 1972-01-13 1979-08-28 Gfe Gesellschaft Fur Elektrometallurgie Mit Beschrankter Haftung Method of rapidly decarburizing ferro- alloys with oxygen
US3990888A (en) * 1972-10-06 1976-11-09 Uddeholms Aktiebolag Decarburization of a metal melt
US3929458A (en) * 1973-02-07 1975-12-30 Creusot Loire Process for the elaboration of chrome steels
US3909245A (en) * 1973-03-30 1975-09-30 Maximilianshuette Eisenwerk Process for lowering the iron content in nickel melts
US3891429A (en) * 1973-06-07 1975-06-24 Koppers Co Inc Method for selective decarburization of alloy steels
US3907548A (en) * 1973-07-04 1975-09-23 Krupp Ag Huettenwerke Process for the production of steels having high chromium content and lowest possible carbon content
US3992194A (en) * 1974-04-11 1976-11-16 Creusot-Loire Method and apparatus for use in the treatment of metals in the liquid state
US3985550A (en) * 1975-01-23 1976-10-12 United States Steel Corporation Method of producing low sulfur steel
US4081268A (en) * 1976-04-28 1978-03-28 Creusot-Loire Method of protecting tuyeres for upwardly blowing pure oxygen through the bottom of steel converters
US4141723A (en) * 1976-09-20 1979-02-27 Institut De Recherches De La Siderurgie Francaise (Irsid) Process for producing stainless steel
US4139368A (en) * 1977-10-11 1979-02-13 Pennsylvania Engineering Corporation Metallurgical method
US4168158A (en) * 1977-12-08 1979-09-18 Kawasaki Steel Corporation Method for producing alloy steels having a high chromium content and an extremely low carbon content
US4192675A (en) * 1978-01-17 1980-03-11 S.A. Manganese Amcor Ltd. Process for decarburizing ferro-manganese
US4174212A (en) * 1978-03-10 1979-11-13 A. Finkl & Sons Co. Method for the refining of steel
US4330326A (en) * 1979-08-24 1982-05-18 Eisenwerk-Gesellschaft Maximilianshutte Mbh. Method and a means for introducing close-grained carbonaceous fuels into a molten iron bath
US4385753A (en) * 1980-03-05 1983-05-31 Creusot-Loire Tuyere for the simultaneous and separate introduction of at least one gas and one powder material

Also Published As

Publication number Publication date
FR2042874A5 (enrdf_load_stackoverflow) 1971-02-12
DE1916945C3 (de) 1980-04-17
DE1916945B2 (de) 1975-06-26
GB1271486A (en) 1972-04-19
DE1916945A1 (de) 1970-11-12

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