WO2005069977A2 - Method for producing low carbon steel - Google Patents
Method for producing low carbon steel Download PDFInfo
- Publication number
- WO2005069977A2 WO2005069977A2 PCT/US2005/002102 US2005002102W WO2005069977A2 WO 2005069977 A2 WO2005069977 A2 WO 2005069977A2 US 2005002102 W US2005002102 W US 2005002102W WO 2005069977 A2 WO2005069977 A2 WO 2005069977A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxygen
- stage
- lance
- shroud
- gas
- Prior art date
Links
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
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/30—Regulating or controlling the blowing
- C21C5/32—Blowing from above
-
- 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
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/068—Decarburising
-
- 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
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
-
- 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
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/30—Regulating or controlling the blowing
-
- 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
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/42—Constructional features of converters
- C21C5/46—Details or accessories
- C21C5/4606—Lances or injectors
-
- 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
- C21C2300/00—Process aspects
- C21C2300/02—Foam creation
-
- 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
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/52—Manufacture of steel in electric furnaces
- C21C5/5211—Manufacture of steel in electric furnaces in an alternating current [AC] electric arc furnace
- C21C5/5217—Manufacture of steel in electric furnaces in an alternating current [AC] electric arc furnace equipped with burners or devices for injecting gas, i.e. oxygen, or pulverulent materials into the furnace
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- This invention relates generally to steelmaking wherein oxygen is provided to molten steel from above the surface of the molten steel and, more particularly, to the employment of such procedure for the production of low carbon steel .
- the basic oxygen furnace is a well- known steelmaking method used to produce most of the world's high-quality low carbon steel.
- the BOF process uses molten iron from a blast furnace as the primary iron source. Because of the nature of the blast furnace process, this molten blast furnace iron is saturated with dissolved carbon. In the BOF process, this molten iron is charged along with steel scrap into an open-top converter. A water-cooled lance is inserted through the top opening and oxygen is blown from the lance in multiple jets toward the molten metal . This oxygen burns the carbon contained in the molten iron, melting the scrap, and creating a bath of liquid steel.
- the rate at which carbon is burned by the oxygen determines the productivity of the BOF process.
- carbon oxidation occurs as quickly as oxygen can be blown through the lance to the liquid steel bath.
- the rate of carbon oxidation depends on the transport of dissolved carbon from the bulk of the steel bath to the area where the oxygen jet impacts the bath.
- One problem with the conventional BOF process is that stirring and mixing in the bulk steel bath are relatively poor. As a result, below about 0.30 weight percent carbon, transport of carbon from the bulk bath to the reaction zone is slow and decarburization is inefficient.
- a method for producing low carbon steel comprising the following sequential refining stages : (A) providing oxygen in at least one stream enveloped in a gas shroud from a lance to molten steel having a carbon concentration greater than 0.30 weight percent ; thereafter (B) providing oxygen in at least one stream enveloped in a flame shroud from the lance to the molten steel; and thereafter (C) providing oxygen and inert gas in at least one stream enveloped in a flame shroud from the lance to the molten steel; said refining stages serving to produce low carbon steel .
- a method for producing low carbon steel comprising the following sequential refining stages: (A) providing oxygen in at least one stream enveloped in a gas shroud from a lance to molten steel having a carbon concentration greater than 0.30 weight percent; thereafter (B) providing oxygen in at least one stream enveloped in a flame shroud from the lance to the molten steel; and thereafter (C) providing inert gas in at least one stream enveloped in a flame shroud from the lance to the molten steel; said refining stages serving to produce low carbon steel .
- low carbon steel means steel having a carbon concentration less than 0.10 weight percent.
- inert gas means one or more of argon, nitrogen, carbon monoxide, carbon dioxide and helium.
- gas shroud means a non-combusting gaseous envelope around and along one or more gas streams .
- flame shroud means a combusting gaseous envelope around and along one or more gas streams .
- coherent jet means a supersonic gas stream which has little or no increase in diameter in its flow direction.
- conventional jet means a supersonic gas stream which has an increase in diameter in its flow direction.
- Figure 1 is a head on view of one particularly preferred lance for use in the practice of this invention.
- Figure 2 is a cross sectional view of the particularly preferred lance for use in the practice of this invention.
- Figure 3 is a generalized representation of the method of this invention in operation.
- Figure 4 is a graphical representation of results obtained with the practice of this invention compared with results obtained with two known practices .
- the invention is a method employing three different stages in a specified order whereby low carbon steel is produced by the provision of oxygen to molten steel from above the surface of the molten steel .
- the oxygen reacts with the carbon in the molten steel within a converter to produce carbon dioxide and carbon monoxide which bubble out of the molten steel, thus lowering the carbon concentration and producing low carbon steel .
- the invention will be described in greater detail with reference to the drawings. The numerals in the drawings are the same for the common elements.
- the charge 15 prior to the start of the three stage refining process of this invention has a carbon concentration greater than 0.30 weight percent, and typically has a carbon concentration within the range of from 4.0 to 4.5 weight percent .
- the first stage of the refining method of this invention comprises from about 30 to about 70 percent of the refining period, i.e. about 30 to about 70 percent of the total oxygen provided to the molten steel during the refining method of this invention is provided during the first stage. Fluxes such as lime and dolomite are added at the beginning of the refining period to achieve the desired chemistry of the slag 12 and to neutralize the silicon dioxide which is formed during the first stage.
- oxygen is provided in at least one stream from the lance tip or lance face to the molten steel .
- a gas shroud envelops the oxygen streams .
- the gas shroud extends from the lance tip to the molten steel surface.
- the gas shroud comprises oxygen and inert gas .
- the inert gas for the gas shroud is nitrogen.
- Figures 1 and 2 illustrate a preferred apparatus for the practice of each of the three stages of the refining method of this invention.
- oxygen is provided from four nozzles 2 through four nozzle openings 4 on lance face 6 of lance 3.
- a ring 20 of ports in a recession 21 surrounds the nozzles at the lance tip, and the oxygen and inert gas for forming the gas shroud is provided from these ports.
- oxygen is provided from a first set of ports, e.g. 22, and inert gas is provided from a second set of ports, e.g. 23, which alternate with the ports of the first set .
- the gas shroud around the oxygen streams causes the gas streams to form conventional jets.
- the conventional supersonic jets rapidly decay to subsonic velocities at which point the jet spreads with a half angle of about 10 degrees resulting in a less penetrating jet and a large area of surface contact with the surrounding atmosphere and the bath.
- Such oxygen streams are less likely to be reflected by unmelted scrap that is present during the beginning of the refining period which would cause damage to the lance or to the converter lining.
- the first stage of the refining method of this invention is concluded and the second stage is initiated.
- oxygen is provided in at least one stream from the lance tip or lance face to the molten steel .
- a flame shroud envelops the oxygen stream or streams .
- the flame shroud extends from the lance tip to the molten steel surface.
- any suitable fuel may be used to produce the flame shroud in the practice of this invention.
- the fuel is a hydrogen-containing fuel.
- such fuels one can name methane, natural gas, propane, butane, petroleum gas, coke-oven gas, gasified or vaporized fuel oils and hydrogen and mixtures thereof. Mixtures of hydrogen-containing fuels with carbon monoxide or inert gases can also be used.
- the fuel for the flame shroud is preferably provided from the ports through which the inert gas was provided during the first stage, and the oxygen for the flame shroud is preferably provided from the same ports it was provided for the gas shroud during the first stage .
- the refining oxygen during the second stage is provided through the same nozzles as during the first stage.
- the flame shroud around the oxygen stream or streams during the second stage of the refining method of this invention causes the oxygen stream or streams to form coherent oxygen jets.
- the coherent jet or jets extend from the lance tip to the surface of the molten steel .
- Basic oxygen furnaces often suffer from ejection of metal and slag from the furnace due to rapid reaction of oxygen and FeO in the slag with carbon, resulting in high rates of carbon monoxide evolution which entrain the metal and slag and carry it out of the vessel.
- the rate limiting step for carbon removal changes from the rate of oxygen injection (total 0 2 flow rate through lance) to mass transfer of carbon within the bath.
- Switching from conventional to coherent jets increases the mass transfer rate of carbon in the bath because of the increased bath mixing provided by the more deeply penetrating jets. This results in more efficient carbon removal and less formation of FeO resulting in improved Fe yield.
- the specific point in the blow at which the switch from the first stage to the second stage is made is based on the silicon content of the hot metal and the relative importance of each of the above factors for both the conventional and coherent jet operating modes and overall optimization of furnace operation and cost .
- the molten steel has a carbon concentration generally less than 0.3 weight percent and typically within the range of from 0.3 to 0.02 weight percent .
- the third stage of the refining method of this invention is initiated.
- inert gas, or oxygen and inert gas wherein the inert gas comprises at least 10 mole percent of the oxygen and inert gas is provided in at least one stream from the lance tip or lance face to the molten steel .
- a flame shroud envelops the stream or streams .
- the flame shroud extends from the lance tip to the molten steel surface.
- the flame shroud is formed in a manner similar to the manner that it is formed during the second stage of the refining method of this invention.
- the inert gas, or oxygen and inert gas, provided during the third stage of the refining method of this invention is provided through nozzles 2.
- the preferred inert gas employed during the third stage of the refining method of this invention is argon.
- the flame shroud around the inert gas, or oxygen and inert gas, stream or streams during the third stage of the refining method of this invention causes the inert gas, or oxygen and inert gas, stream or streams to form coherent jets.
- the coherent jet or jets extend from the lance tip to the surface of the molten steel .
- the molten steel has a carbon concentration less than 0.10 weight percent.
- element 16 is a generalized representation of the central stream or streams, i.e. oxygen in the first and second stages and inert gas or oxygen and inert gas in the third stage, and the shrouds, i.e. gas shroud during the first stage and flame shroud during the second and third stages, employed in the practice of the refining method of this invention.
- the use of the third stage of the practice of this invention in conjunction with the first and second stages serves to reduce inhomogeneous zones in chemical composition and temperature in the molten metal due to lack of proper mixing in the metal bath without excessive metal bath oxidation and slag oxidation.
- beneficial effects of the improved mixing resulting from top-blown coherent jets of inert gas or oxygen- inert gas on low carbon heats include enhanced steel decarburization, decreased FeO content in the slag resulting in better iron yield and reduced slag-induced refractory erosion, reduced dissolved oxygen in the metal resulting in lower aluminum consumption in the ladle, higher manganese content in the metal resulting in lower consumption of ferromanganese, enhanced desulferization and dephosphorization, and reduced hydrogen pickup.
- Figure 4 there is shown a comparison of the level of oxygen dissolved in the refined steel as a function of the final level of dissolved carbon for three practices.
- Curve A illustrates that for a conventional bottom-stirred BOF process with conventional oxygen jets (40,000 Nm 3 /hr) and argon blown through tuyeres in the converter bottom (800 Nm 3 /hr) .
- Curve B illustrates that for a bottom-stirred BOF process with coherent oxygen jets and with argon blown through tuyeres in the converter bottom.
- Curve C illustrates that for the invention which in this example used top blown coherent argon jets instead of blowing argon through tuyeres in the converter bottom.
- the level of dissolved oxygen reflects the amount of metallics which have been oxidized and lost to the slag It also reflects the amount of deoxidant, e.g.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Carbon Steel Or Casting Steel Manufacturing (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006551344A JP4938464B2 (en) | 2004-01-23 | 2005-01-19 | Low carbon steel manufacturing method |
BRPI0506964-5A BRPI0506964B1 (en) | 2004-01-23 | 2005-01-19 | Method for producing low carbon steel |
MXPA06008215A MXPA06008215A (en) | 2004-01-23 | 2005-01-19 | Method for producing low carbon steel. |
AU2005207009A AU2005207009A1 (en) | 2004-01-23 | 2005-01-19 | Method for producing low carbon steel |
KR1020067014692A KR101165104B1 (en) | 2004-01-23 | 2005-01-19 | Method for producing low carbon steel |
CA002555472A CA2555472C (en) | 2004-01-23 | 2005-01-19 | Method for producing low carbon steel |
EP05711864.8A EP1721017B1 (en) | 2004-01-23 | 2005-01-19 | Method for producing low carbon steel |
ES05711864T ES2405998T3 (en) | 2004-01-23 | 2005-01-19 | Method to produce low carbon steel |
PL05711864T PL1721017T3 (en) | 2004-01-23 | 2005-01-19 | Method for producing low carbon steel |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/762,298 | 2004-01-23 | ||
US10/762,298 US6932854B2 (en) | 2004-01-23 | 2004-01-23 | Method for producing low carbon steel |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2005069977A2 true WO2005069977A2 (en) | 2005-08-04 |
WO2005069977A3 WO2005069977A3 (en) | 2006-02-23 |
Family
ID=34794850
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2005/002102 WO2005069977A2 (en) | 2004-01-23 | 2005-01-19 | Method for producing low carbon steel |
Country Status (15)
Country | Link |
---|---|
US (1) | US6932854B2 (en) |
EP (1) | EP1721017B1 (en) |
JP (1) | JP4938464B2 (en) |
KR (1) | KR101165104B1 (en) |
CN (1) | CN100507014C (en) |
AU (1) | AU2005207009A1 (en) |
BR (1) | BRPI0506964B1 (en) |
CA (1) | CA2555472C (en) |
ES (1) | ES2405998T3 (en) |
MX (1) | MXPA06008215A (en) |
PL (1) | PL1721017T3 (en) |
PT (1) | PT1721017E (en) |
TW (1) | TWI333981B (en) |
WO (1) | WO2005069977A2 (en) |
ZA (1) | ZA200605710B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20070012478A (en) * | 2004-05-14 | 2007-01-25 | 더 비오씨 그룹, 인크. | Refining molten metal |
WO2008076901A1 (en) * | 2006-12-15 | 2008-06-26 | Praxair Technology, Inc. | Injection method for inert gas |
DE102008050599B3 (en) * | 2008-10-09 | 2010-07-29 | Uhde Gmbh | Apparatus and method for distributing primary air in coke ovens |
US8377372B2 (en) * | 2009-11-30 | 2013-02-19 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Dynamic lances utilizing fluidic techniques |
US20110127701A1 (en) * | 2009-11-30 | 2011-06-02 | Grant Michael G K | Dynamic control of lance utilizing co-flow fluidic techniques |
US8323558B2 (en) * | 2009-11-30 | 2012-12-04 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Dynamic control of lance utilizing counterflow fluidic techniques |
US10781499B2 (en) * | 2018-01-17 | 2020-09-22 | Air Products And Chemicals, Inc. | Bottom stirring tuyere and method for a basic oxygen furnace |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1092828A (en) * | 1978-10-18 | 1981-01-06 | William E. Creswick | Basic oxygen furnace argon refining blow |
US4373949A (en) * | 1979-02-07 | 1983-02-15 | Union Carbide Corporation | Method for increasing vessel lining life for basic oxygen furnaces |
US4397685A (en) * | 1982-03-26 | 1983-08-09 | Union Carbide Corporation | Production of ultra low carbon steel by the basic oxygen process |
US4599107A (en) * | 1985-05-20 | 1986-07-08 | Union Carbide Corporation | Method for controlling secondary top-blown oxygen in subsurface pneumatic steel refining |
JPH01123016A (en) * | 1987-11-06 | 1989-05-16 | Nkk Corp | Blowing method for converter |
US6125133A (en) * | 1997-03-18 | 2000-09-26 | Praxair, Inc. | Lance/burner for molten metal furnace |
US5814125A (en) * | 1997-03-18 | 1998-09-29 | Praxair Technology, Inc. | Method for introducing gas into a liquid |
US6176894B1 (en) * | 1998-06-17 | 2001-01-23 | Praxair Technology, Inc. | Supersonic coherent gas jet for providing gas into a liquid |
CN1250747C (en) * | 1998-08-28 | 2006-04-12 | 沃斯特-阿尔派因工业设备制造有限公司 | Method for producing a metal melt and corresponding multifunction lance |
US6604037B1 (en) | 1999-03-22 | 2003-08-05 | Continental Teves, Ag & Co. Ohg | Circuit system and method of configuring an interface of a control or regulating device |
US6171544B1 (en) * | 1999-04-02 | 2001-01-09 | Praxair Technology, Inc. | Multiple coherent jet lance |
US6241510B1 (en) * | 2000-02-02 | 2001-06-05 | Praxair Technology, Inc. | System for providing proximate turbulent and coherent gas jets |
US6432163B1 (en) * | 2001-06-22 | 2002-08-13 | Praxair Technology, Inc. | Metal refining method using differing refining oxygen sequence |
US6604937B1 (en) * | 2002-05-24 | 2003-08-12 | Praxair Technology, Inc. | Coherent jet system with single ring flame envelope |
GB0213376D0 (en) * | 2002-06-11 | 2002-07-24 | Boc Group Plc | Refining ferroalloys |
US6773484B2 (en) * | 2002-06-26 | 2004-08-10 | Praxair Technology, Inc. | Extensionless coherent jet system with aligned flame envelope ports |
US6875398B2 (en) * | 2003-01-15 | 2005-04-05 | Praxair Technology, Inc. | Coherent jet system with outwardly angled flame envelope ports |
-
2004
- 2004-01-23 US US10/762,298 patent/US6932854B2/en not_active Expired - Lifetime
- 2004-11-15 TW TW093134963A patent/TWI333981B/en not_active IP Right Cessation
-
2005
- 2005-01-19 KR KR1020067014692A patent/KR101165104B1/en active IP Right Grant
- 2005-01-19 BR BRPI0506964-5A patent/BRPI0506964B1/en not_active IP Right Cessation
- 2005-01-19 CA CA002555472A patent/CA2555472C/en not_active Expired - Fee Related
- 2005-01-19 EP EP05711864.8A patent/EP1721017B1/en not_active Not-in-force
- 2005-01-19 CN CNB2005800031051A patent/CN100507014C/en not_active Expired - Fee Related
- 2005-01-19 PT PT57118648T patent/PT1721017E/en unknown
- 2005-01-19 PL PL05711864T patent/PL1721017T3/en unknown
- 2005-01-19 ES ES05711864T patent/ES2405998T3/en active Active
- 2005-01-19 JP JP2006551344A patent/JP4938464B2/en not_active Expired - Fee Related
- 2005-01-19 MX MXPA06008215A patent/MXPA06008215A/en active IP Right Grant
- 2005-01-19 AU AU2005207009A patent/AU2005207009A1/en not_active Abandoned
- 2005-01-19 WO PCT/US2005/002102 patent/WO2005069977A2/en active Application Filing
-
2006
- 2006-07-11 ZA ZA200605710A patent/ZA200605710B/en unknown
Non-Patent Citations (1)
Title |
---|
See references of EP1721017A4 * |
Also Published As
Publication number | Publication date |
---|---|
EP1721017A2 (en) | 2006-11-15 |
CA2555472C (en) | 2009-04-21 |
CN1910295A (en) | 2007-02-07 |
MXPA06008215A (en) | 2006-09-06 |
US6932854B2 (en) | 2005-08-23 |
JP2007518883A (en) | 2007-07-12 |
US20050160876A1 (en) | 2005-07-28 |
WO2005069977A3 (en) | 2006-02-23 |
TWI333981B (en) | 2010-12-01 |
ZA200605710B (en) | 2008-01-30 |
PT1721017E (en) | 2013-07-26 |
PL1721017T3 (en) | 2013-09-30 |
KR101165104B1 (en) | 2012-07-12 |
TW200525041A (en) | 2005-08-01 |
CA2555472A1 (en) | 2005-08-04 |
ES2405998T3 (en) | 2013-06-04 |
EP1721017B1 (en) | 2013-04-24 |
BRPI0506964A (en) | 2007-07-03 |
CN100507014C (en) | 2009-07-01 |
JP4938464B2 (en) | 2012-05-23 |
AU2005207009A1 (en) | 2005-08-04 |
EP1721017A4 (en) | 2010-01-20 |
KR20060130124A (en) | 2006-12-18 |
BRPI0506964B1 (en) | 2015-08-04 |
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