US3929464A - Desulfurization of molten ferrous metals - Google Patents

Desulfurization of molten ferrous metals Download PDF

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Publication number
US3929464A
US3929464A US393505A US39350573A US3929464A US 3929464 A US3929464 A US 3929464A US 393505 A US393505 A US 393505A US 39350573 A US39350573 A US 39350573A US 3929464 A US3929464 A US 3929464A
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US
United States
Prior art keywords
calcium carbide
molten iron
injection
iron
gas stream
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
US393505A
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English (en)
Inventor
Lamar S Todd
Alan Fitzgibbon
Michael C Carosella
Donald C Hilty
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.)
Elkem Metals Co LP
Original Assignee
Union Carbide Corp
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 Union Carbide Corp filed Critical Union Carbide Corp
Priority to US393505A priority Critical patent/US3929464A/en
Priority to CA207,037A priority patent/CA1024748A/en
Priority to DE2440205A priority patent/DE2440205B2/de
Priority to NO743126A priority patent/NO743126L/no
Priority to SE7411025A priority patent/SE7411025L/xx
Priority to FR7429677A priority patent/FR2242468B1/fr
Priority to IT52823/74A priority patent/IT1019175B/it
Priority to GB3797774A priority patent/GB1476182A/en
Priority to JP9984374A priority patent/JPS5624009B2/ja
Priority to BE148117A priority patent/BE819430A/xx
Application granted granted Critical
Publication of US3929464A publication Critical patent/US3929464A/en
Assigned to ELKEM METALS COMPANY, A NEW YORK GENERAL PARTNERSHIP reassignment ELKEM METALS COMPANY, A NEW YORK GENERAL PARTNERSHIP ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: UNION CARBIDE CORPORATION, A NY CORP.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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

Definitions

  • the present invention relates to a method of reducing the sulfur impurity of molten ferrous metals. More particularly, the present invention is directed to the I desulfurization of molten iron through the injection therein of calcium carbide.
  • a method in accordance with the present invention comprises the injection of very finely divided calcium carbide in a gas stream at moderate velocities well below the surface of a bath of molten iron, whereby the sulfur content of the iron is efficiently reduced to 0.015% and lower without the requirement of followup agitation treatment.
  • the present invention is suitable for the treatment of tonnage quantities of molten iron.
  • finely divided calcium carbide is provided, substantially all of which is not larger than 200 microns, at least about 50 percent being not larger than about 50 microns and at least about percent being not larger than about 10 microns; and the aggregate of the finely divided calcium carbide having a Fischer sub-sieve number of of less than about 12.0.
  • the preferred sizing for the finely divided calcium carbide is substantially all not larger than 200 microns, at least about 60 percent being not larger than about 50 microns and at least about percent being not larger than about 10 microns, and the aggregate of the finely divided calcium carbide having a Fischer sub-sieve number of less than 7.5.
  • Calcium carbide material of this nature can be prepared by milling commercially available calcium carbide, e.g. fine grade calcium carbide, the particles of which are substantially all in the range of 0.6 millimeter to 0.074 millimeter.
  • Finely divided calcium carbide having the sizing described above in accordance with the present invention can be readily injected into molten iron using a device of the type schematically illustrated in FIG. 1.
  • finely divided calcium carbide powder 1 is charged from container 2 via valve 3 into dispensing vessel 5 having at its lower portion a conventional fluidizing mechanism indicated at 7, which can be one of the various commercially available devices.
  • Fluidizing gas e.g. nitrogen
  • transport injection gas which can be nitrogen, or any other gas or moisture free gas such as dry air is introduced via valve 11 and carries the finely divided calcium carbide through flexible hose conduit 13 into lance 15, suitable made of 1 /4 inches l.D. standard extra-heavy steel pipe protected by refractory brick sleeve 17.
  • lance 15 is positioned in vessel 19, shown as a conventional torpedo car, and immersed in sulfur-containing molten pig iron 21 covered by a slag layer 23.
  • the vessel illustrated ordinarily contains from about 100 to 250 tons of molten metal at depths of from 4 to 9 feet.
  • the ratio by weight of calcium carbide to injection gas is maintained in the range of to 140 because a ratio less than about 75 results in excessively long injection times and a ratio greater than 140 results in undesirably poor desulfurization efficiency.
  • the calcium carbide containing gas is injected in the lower 75 percent of the depth of the molten iron. In actual practice the lower 10 percent has provided excellent results.
  • the velocity of the gas entering the molten iron is preferably in the range of about 5 to 15 feet per second.
  • the injection of calcium carbide was continued for 8 minutes 45 seconds at which time the temperature of the molten iron was about 2510F. at the end of this treatment the sulfur content of the iron was 0.015%.
  • the total amount of finely divided material injected into the iron was 9.4 lbs. per ton of iron (2.95 lbs. per ton of iron per 0.01% S); the rate of injection was'134.9 pounds per minute.
  • the calcium carbide efficiency based on the CaC content of the material was 22.9%.
  • the average calcium carbide efficiency based on the CaC, content of the material used was about 21.5%
  • finely vdivided particles of calcium carbide in a gas stream substantially all of said finely divided particles of calcium carbide being not larger than 200 microns, at least about 50 percent of said particles being not; larger than 50 microns and at least 20 percent being not larger than 10 microns and the aggregate of said particles of calcium carbide having a Fischer sub-sieve number of less than about 12.

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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)
US393505A 1973-08-31 1973-08-31 Desulfurization of molten ferrous metals Expired - Lifetime US3929464A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US393505A US3929464A (en) 1973-08-31 1973-08-31 Desulfurization of molten ferrous metals
CA207,037A CA1024748A (en) 1973-08-31 1974-08-14 Desulfurization of molten ferrous metals
DE2440205A DE2440205B2 (de) 1973-08-31 1974-08-22 Verfahren zur Herabsetzung des Schwefelgehalts von geschmolzenem Eisen
SE7411025A SE7411025L (xx) 1973-08-31 1974-08-30
FR7429677A FR2242468B1 (xx) 1973-08-31 1974-08-30
IT52823/74A IT1019175B (it) 1973-08-31 1974-08-30 Procedimento per la desolforazione di metalli ferrosi
NO743126A NO743126L (xx) 1973-08-31 1974-08-30
GB3797774A GB1476182A (en) 1973-08-31 1974-08-30 Desulphurization of molten ferrous metals
JP9984374A JPS5624009B2 (xx) 1973-08-31 1974-08-30
BE148117A BE819430A (fr) 1973-08-31 1974-08-30 Procede de reduction de la teneur en soufre des metaux ferreux fondus

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US393505A US3929464A (en) 1973-08-31 1973-08-31 Desulfurization of molten ferrous metals

Publications (1)

Publication Number Publication Date
US3929464A true US3929464A (en) 1975-12-30

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Family Applications (1)

Application Number Title Priority Date Filing Date
US393505A Expired - Lifetime US3929464A (en) 1973-08-31 1973-08-31 Desulfurization of molten ferrous metals

Country Status (10)

Country Link
US (1) US3929464A (xx)
JP (1) JPS5624009B2 (xx)
BE (1) BE819430A (xx)
CA (1) CA1024748A (xx)
DE (1) DE2440205B2 (xx)
FR (1) FR2242468B1 (xx)
GB (1) GB1476182A (xx)
IT (1) IT1019175B (xx)
NO (1) NO743126L (xx)
SE (1) SE7411025L (xx)

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998625A (en) * 1975-11-12 1976-12-21 Jones & Laughlin Steel Corporation Desulfurization method
US4049442A (en) * 1975-01-08 1977-09-20 Suddeutsche Kalkstickstoff-Werke Aktiengesellschaft Composition for desulfurizing iron melts
US4067729A (en) * 1976-09-01 1978-01-10 Wolfgang Holzgruber Desulfurization of liquid iron melts
US4139369A (en) * 1976-09-17 1979-02-13 Hoechst Aktiengesellschaft Desulphurization of an iron melt
US4169724A (en) * 1977-02-26 1979-10-02 Skw Trostberg Aktiengesellschaft Desulfurization of iron melts
US4174965A (en) * 1977-06-02 1979-11-20 Swiss Aluminium Ltd. Process for the production of metal alloys
US4182626A (en) * 1977-06-25 1980-01-08 Hoechst Aktiengesellschaft Production of granular compositions containing pulverulent magnesium
US4194903A (en) * 1976-10-12 1980-03-25 Hoesch Werke Aktiengesellschaft Method of producing steel with the lowest possible sulfur content by desulfurization of pig iron with magnesium coke
US4194902A (en) * 1977-09-15 1980-03-25 Skw Trostberg Aktiengesellschaft Desulfurization agent for ferrous melts and method of using the same
US4198229A (en) * 1976-06-28 1980-04-15 Nippon Steel Corporation Method of dephosphorization of metal or alloy
US4199350A (en) * 1975-05-17 1980-04-22 Vacmetal Gesellschaft fur Vakuummetallurgie mbH Method for the production of quality steels
US4200458A (en) * 1978-09-06 1980-04-29 Scandinavian Lancers Aktiebolag Method for the alloying of a metal melt
US4232854A (en) * 1978-05-26 1980-11-11 Barbakadze Dzhondo F Method of introducing powdered reagents into molten metals and apparatus for effecting same
US4242126A (en) * 1979-07-11 1980-12-30 Skw Trostberg Aktiengesellschaft Process for the treatment of iron melts and for increasing the scrap portion in the converter
US4260417A (en) * 1979-11-05 1981-04-07 Ford Motor Company Batch desulfurization in a coreless induction furnace
US4266969A (en) * 1980-01-22 1981-05-12 Jones & Laughlin Steel Corporation Desulfurization process
US4277279A (en) * 1980-03-24 1981-07-07 Jones & Laughlin Steel Corporation Method and apparatus for dispensing a fluidized stream of particulate material
US4286774A (en) * 1980-04-22 1981-09-01 Victor Benatar System for automatically injecting a measured quantity of powdered reagent into a pool of molten metal
US4315773A (en) * 1979-11-27 1982-02-16 Skw Trostberg Aktiengesellschaft Desulfurization mixture and process for desulfurizing pig iron
US4347078A (en) * 1978-12-21 1982-08-31 Arbed S.A. Process and apparatus for the desulfurizing of iron melts
US4374664A (en) * 1979-02-16 1983-02-22 Nippon Steel Corporation Process for desulfurizing molten pig iron
US4395281A (en) * 1980-12-23 1983-07-26 Asea Ab Treating molten pig iron in a torpedo
USRE31676E (en) 1982-09-29 1984-09-18 Thyssen Aktiengesellschaft vorm August Thyssen-Hutte AG Method and apparatus for dispensing a fluidizable solid from a pressure vessel
US4483710A (en) * 1981-03-31 1984-11-20 Union Carbide Corporation Addition agent for adding vanadium to iron base alloys
FR2560216A1 (fr) * 1984-02-24 1985-08-30 Clecim Sa Procede et dispositif de desulfuration de la fonte liquide
US4592777A (en) * 1984-05-16 1986-06-03 Thyssen Stahl Ag Method, process and composition for desulfurizing pig-iron melts
US4738715A (en) * 1987-01-02 1988-04-19 Hart Metals, Inc. Desulfurizing reagent for hot metal
US4741771A (en) * 1985-12-06 1988-05-03 Centro Sperimentale Metallurgico S.P.A. Process for reduction of impurities content of hot metal
US4997167A (en) * 1988-08-04 1991-03-05 Elkem A/S Ladle inoculant dispenser
US5021086A (en) * 1990-07-05 1991-06-04 Reactive Metals And Alloys Corporation Iron desulfurization additive and method for introduction into hot metal
US5336293A (en) * 1992-08-13 1994-08-09 Alfred Freissmuth Desulfurizing agent for pig iron and cast iron, and process for desulfurization
US5358550A (en) * 1992-10-26 1994-10-25 Rossborough Manufacturing Company Desulfurization agent
US6352570B1 (en) 2000-04-10 2002-03-05 Rossborough Manufacturing Co., Lp Magnesium desulfurization agent
US6395058B2 (en) 2000-04-10 2002-05-28 Rossborough Manufacturing Co. L.P. Method of alloying ferrous material with magnesium injection agent
US20040074339A1 (en) * 2002-10-18 2004-04-22 Rossborough Manufacturing Company, A Delaware Corporation Process for magnesium granules
US20040083851A1 (en) * 2002-10-30 2004-05-06 Rossborough Manufacturing Company, A Delaware Corporation Reclaimed magnesium desulfurization agent
US6802894B2 (en) 1998-12-11 2004-10-12 Jeneric/Pentron Incorporated Lithium disilicate glass-ceramics
US20070221012A1 (en) * 2006-03-27 2007-09-27 Magnesium Technologies Corporation Scrap bale for steel making process
US20080196548A1 (en) * 2007-02-16 2008-08-21 Magnesium Technologies Corporation Desulfurization puck

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2656522C2 (de) * 1976-12-14 1978-11-09 Stahlwerke Peine-Salzgitter Ag, 3150 Peine Verfahren zur Entschwefelung von Roheisen
US4180397A (en) * 1977-09-15 1979-12-25 British Steel Corporation Machinable steel
DE2934193A1 (de) * 1979-08-23 1981-03-26 Denki Kagaku Kogyo K.K., Tokio/Tokyo Mittel zur entschwefelung von geschmolzenem eisen.
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.
FR2699931B1 (fr) * 1992-12-31 1995-03-31 Lorraine Laminage Procédé de désulfuration de la fonte en poche.

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2803533A (en) * 1954-05-03 1957-08-20 Union Carbide Corp Method of injecting fluidized powders for metallurgical treatment

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5042085Y2 (xx) * 1971-03-04 1975-11-29

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2803533A (en) * 1954-05-03 1957-08-20 Union Carbide Corp Method of injecting fluidized powders for metallurgical treatment

Cited By (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049442A (en) * 1975-01-08 1977-09-20 Suddeutsche Kalkstickstoff-Werke Aktiengesellschaft Composition for desulfurizing iron melts
US4199350A (en) * 1975-05-17 1980-04-22 Vacmetal Gesellschaft fur Vakuummetallurgie mbH Method for the production of quality steels
US3998625A (en) * 1975-11-12 1976-12-21 Jones & Laughlin Steel Corporation Desulfurization method
US4198229A (en) * 1976-06-28 1980-04-15 Nippon Steel Corporation Method of dephosphorization of metal or alloy
US4067729A (en) * 1976-09-01 1978-01-10 Wolfgang Holzgruber Desulfurization of liquid iron melts
US4139369A (en) * 1976-09-17 1979-02-13 Hoechst Aktiengesellschaft Desulphurization of an iron melt
US4194903A (en) * 1976-10-12 1980-03-25 Hoesch Werke Aktiengesellschaft Method of producing steel with the lowest possible sulfur content by desulfurization of pig iron with magnesium coke
US4169724A (en) * 1977-02-26 1979-10-02 Skw Trostberg Aktiengesellschaft Desulfurization of iron melts
US4174965A (en) * 1977-06-02 1979-11-20 Swiss Aluminium Ltd. Process for the production of metal alloys
US4182626A (en) * 1977-06-25 1980-01-08 Hoechst Aktiengesellschaft Production of granular compositions containing pulverulent magnesium
US4194902A (en) * 1977-09-15 1980-03-25 Skw Trostberg Aktiengesellschaft Desulfurization agent for ferrous melts and method of using the same
US4232854A (en) * 1978-05-26 1980-11-11 Barbakadze Dzhondo F Method of introducing powdered reagents into molten metals and apparatus for effecting same
US4200458A (en) * 1978-09-06 1980-04-29 Scandinavian Lancers Aktiebolag Method for the alloying of a metal melt
US4347078A (en) * 1978-12-21 1982-08-31 Arbed S.A. Process and apparatus for the desulfurizing of iron melts
US4374664A (en) * 1979-02-16 1983-02-22 Nippon Steel Corporation Process for desulfurizing molten pig iron
US4242126A (en) * 1979-07-11 1980-12-30 Skw Trostberg Aktiengesellschaft Process for the treatment of iron melts and for increasing the scrap portion in the converter
US4260417A (en) * 1979-11-05 1981-04-07 Ford Motor Company Batch desulfurization in a coreless induction furnace
US4315773A (en) * 1979-11-27 1982-02-16 Skw Trostberg Aktiengesellschaft Desulfurization mixture and process for desulfurizing pig iron
US4266969A (en) * 1980-01-22 1981-05-12 Jones & Laughlin Steel Corporation Desulfurization process
US4277279A (en) * 1980-03-24 1981-07-07 Jones & Laughlin Steel Corporation Method and apparatus for dispensing a fluidized stream of particulate material
US4286774A (en) * 1980-04-22 1981-09-01 Victor Benatar System for automatically injecting a measured quantity of powdered reagent into a pool of molten metal
US4395281A (en) * 1980-12-23 1983-07-26 Asea Ab Treating molten pig iron in a torpedo
US4483710A (en) * 1981-03-31 1984-11-20 Union Carbide Corporation Addition agent for adding vanadium to iron base alloys
USRE31676E (en) 1982-09-29 1984-09-18 Thyssen Aktiengesellschaft vorm August Thyssen-Hutte AG Method and apparatus for dispensing a fluidizable solid from a pressure vessel
FR2560216A1 (fr) * 1984-02-24 1985-08-30 Clecim Sa Procede et dispositif de desulfuration de la fonte liquide
US4592777A (en) * 1984-05-16 1986-06-03 Thyssen Stahl Ag Method, process and composition for desulfurizing pig-iron melts
US4741771A (en) * 1985-12-06 1988-05-03 Centro Sperimentale Metallurgico S.P.A. Process for reduction of impurities content of hot metal
US4738715A (en) * 1987-01-02 1988-04-19 Hart Metals, Inc. Desulfurizing reagent for hot metal
US4997167A (en) * 1988-08-04 1991-03-05 Elkem A/S Ladle inoculant dispenser
US5021086A (en) * 1990-07-05 1991-06-04 Reactive Metals And Alloys Corporation Iron desulfurization additive and method for introduction into hot metal
US5336293A (en) * 1992-08-13 1994-08-09 Alfred Freissmuth Desulfurizing agent for pig iron and cast iron, and process for desulfurization
US5358550A (en) * 1992-10-26 1994-10-25 Rossborough Manufacturing Company Desulfurization agent
US6802894B2 (en) 1998-12-11 2004-10-12 Jeneric/Pentron Incorporated Lithium disilicate glass-ceramics
US6395058B2 (en) 2000-04-10 2002-05-28 Rossborough Manufacturing Co. L.P. Method of alloying ferrous material with magnesium injection agent
US6383249B2 (en) 2000-04-10 2002-05-07 Rossborough Manufacturing Co. Lp Magnesium desulfurization agent
US6352570B1 (en) 2000-04-10 2002-03-05 Rossborough Manufacturing Co., Lp Magnesium desulfurization agent
US20040074339A1 (en) * 2002-10-18 2004-04-22 Rossborough Manufacturing Company, A Delaware Corporation Process for magnesium granules
US6770115B2 (en) 2002-10-18 2004-08-03 Remacor, Inc. Process for magnesium granules
US20040083851A1 (en) * 2002-10-30 2004-05-06 Rossborough Manufacturing Company, A Delaware Corporation Reclaimed magnesium desulfurization agent
US6989040B2 (en) 2002-10-30 2006-01-24 Gerald Zebrowski Reclaimed magnesium desulfurization agent
US20060021467A1 (en) * 2002-10-30 2006-02-02 Magnesium Technologies, Inc. Reclaimed magnesium desulfurization agent
US20070221012A1 (en) * 2006-03-27 2007-09-27 Magnesium Technologies Corporation Scrap bale for steel making process
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

Also Published As

Publication number Publication date
NO743126L (xx) 1975-03-24
FR2242468A1 (xx) 1975-03-28
JPS5051409A (xx) 1975-05-08
DE2440205A1 (de) 1975-03-27
JPS5624009B2 (xx) 1981-06-03
SE7411025L (xx) 1975-03-03
FR2242468B1 (xx) 1978-06-09
IT1019175B (it) 1977-11-10
CA1024748A (en) 1978-01-24
BE819430A (fr) 1975-02-28
DE2440205B2 (de) 1979-10-18
GB1476182A (en) 1977-06-10

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AS Assignment

Owner name: ELKEM METALS COMPANY, 270 PARK AVENUE, NEW YORK, N

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:UNION CARBIDE CORPORATION, A NY CORP.;REEL/FRAME:003882/0761

Effective date: 19810626

Owner name: ELKEM METALS COMPANY, A NEW YORK GENERAL PARTNERSH

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:UNION CARBIDE CORPORATION, A NY CORP.;REEL/FRAME:003882/0761

Effective date: 19810626