US3598573A - Desulfurization agent and process - Google Patents
Desulfurization agent and process Download PDFInfo
- Publication number
- US3598573A US3598573A US819997A US3598573DA US3598573A US 3598573 A US3598573 A US 3598573A US 819997 A US819997 A US 819997A US 3598573D A US3598573D A US 3598573DA US 3598573 A US3598573 A US 3598573A
- Authority
- US
- United States
- Prior art keywords
- desulfurization
- precipitated
- weight
- calcium
- calcium carbonate
- 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
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
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/02—Dephosphorising or desulfurising
- C21C1/025—Agents used for dephosphorising or desulfurising
Definitions
- This invention relates to an improvement in desulfurization agent for ferrous melts, e.g., pig iron, cast iron and steel melts, and to an improved desulfurization process.
- ferrous melts e.g., pig iron, cast iron and steel melts
- precipitated, carbon-containing calcium carbonate refers to a mixture consisting essentially of finely divided calcium carbonate and carbon such as that obtained in the preparation of a dicyandiamide product, in the course of which an aqueous calcium cyanamide' suspension is treated with carbon dioxide to precipitate the calcium carbonate in a very finely divided state intimately admixed with finely divided and co-precipitated carbon.
- This precipitate contains about 70 to 85% by weight calcium carbonate and about 8 to 12% carbon in addition to minor proportions of impurities, especially ferric oxide, aluminum oxide and silicon dioxide.
- the desulfurizing agent of the invention is added to a ferrous melt in an amount that depends upon the initial and desired final sulfur contents of the melt.
- ordinary initial sulfur contents of the order of about 0.04 to 0.06% by weight
- 1.3 kg. desulfurizing agent per ton of melt suffices to reduce the sulfur content by about 0.010%
- approximately 1.7 kg. per ton is required to obtain the same effect of reducing the sulfur content by about 0.01% at melt temperatures of the order of 1200 to 1400 C.
- the desulfurizing agent of the invention is that it is available in very finely divided form. It is, therefore, entirely practical to add it to the melt by blowing or by stirring it in, the latter being accomplished with a shaking pan or a mechanical stirring device. Basically, however, introduction of the desulfurizing agent may take place in a manner suitable to any other pulverulent material and can also take place in the furnace.
- the precipitated calcium carbonate has a structure which is particularly favorable for desulfurization due, perhaps, to increased intimate mixing and contact between the iron in the melt and the calcium carbide promoted by generation of carbon dioxide.
- the finely divided carbon contained in the precipitated carbonate compensates for the slight decarbonization that takes place with desulfurization and, at the same time, provides the reducing conditions required for desulfurization.
- the desulfurizing agent of the invention is positive in its desulfurizing function and is also more economical to use because the losses of iron into the slag are thereby reduced.
- the efficiency with which the calcium carbide component of the combination is consumed, as compared with the consumption of calcium carbide when used alone, is significantly greater.
- EXAMPLE 1 (Prior art) Charges of approximately 35 metric tons pig iron each were desulfurized at between 1260 and 1380 C. with a commercial grade of calcium carbide having a CaC content of approximately by weight introduced into the melt with predried air at 5 atmospheres pressure as carrier gas.
- the carbide had granule sizes of 0.3 to 0.7 mm. in Charges Nos. 1 to 9 and 0.06 to 0.08 mm. in Charges Nos. 10 to 15.
- the amounts of carbide charged, the sulfur contents of the melt before and after desulfurization, and the efliciency were:
- Example 2 The procedure in Example 1 was repeated, all conditions remaining the same except that the desulfurization agent used was a mixture of (A) 80% by weight of the same commercial grade calcium carbide having a CaC content of approximately 80%, and (B) 20% by weight precipitated calcium carbonate containing approximately 75% by weight CaCO 12% by weight carbon and the remainder Fe O A1 0 and SiO impurities.
- the carbide had granule sizes of 0.06 to 0.08 mm. and the precipitated carbonate had granule sizes of less than 0.06 mm.
- the desulfurization agent used was a mixture of (A) 80% by weight of the same commercial grade calcium carbide having a CaC content of approximately 80%, and (B) 20% by weight precipitated calcium carbonate containing approximately 75% by weight CaCO 12% by weight carbon and the remainder Fe O A1 0 and SiO impurities.
- the carbide had granule sizes of 0.06 to 0.08 mm. and the precipitated carbonate had granule sizes of less than
- a desulfurization agent for ferrous melts essentially consisting of from about to about 98% by weight calcium carbide and from about 2 to 40% by weight precipitated, carbon-containing calcium carbonate.
- a process for desulfurizing a sulfur-containing ferrous melt which comprises treating said melt with between about 1.3 and 1.7 kg. of a desulfurization agent per ton of iron melt per 0.01% desired reduction in sulfur content, said desulfurization agent consisting essentially of from about 60 to about 98% by weight calcium carbide and from about 2 to about 40% by weight precipitated, carbon-containing calcium carbonate.
Landscapes
- 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)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19681758250 DE1758250B1 (de) | 1968-04-29 | 1968-04-29 | Mittel zum Entschwefeln von Eisenschmelzen |
Publications (1)
Publication Number | Publication Date |
---|---|
US3598573A true US3598573A (en) | 1971-08-10 |
Family
ID=5694942
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US819997A Expired - Lifetime US3598573A (en) | 1968-04-29 | 1969-04-28 | Desulfurization agent and process |
Country Status (9)
Country | Link |
---|---|
US (1) | US3598573A (xx) |
AT (1) | AT297768B (xx) |
BE (1) | BE730577A (xx) |
CH (1) | CH514677A (xx) |
DE (1) | DE1758250B1 (xx) |
FR (1) | FR2007154A1 (xx) |
GB (1) | GB1226088A (xx) |
LU (1) | LU58448A1 (xx) |
SE (1) | SE341196B (xx) |
Cited By (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3716352A (en) * | 1969-10-24 | 1973-02-13 | Kawasaki Steel Co | Sintered desulfurizer for off-furnace use |
US3884679A (en) * | 1973-05-24 | 1975-05-20 | Sueddeutsche Kalkstickstoff | Method of preparing a stable mixture of calcium with a compound yielding water at elevated temperature |
US3885957A (en) * | 1972-03-01 | 1975-05-27 | Thyssen Niederrhein Ag | Method for the desulfurization of a steel melt |
US3954446A (en) * | 1974-02-23 | 1976-05-04 | Kubota Ltd. | Method of producing high duty cast iron |
US3955966A (en) * | 1974-03-06 | 1976-05-11 | August Thyssen-Hutte Ag | Method for dispensing a fluidizable solid from a pressure vessel |
US3992195A (en) * | 1974-04-20 | 1976-11-16 | Thyssen Niederrhein Ag Hutten- Und Walzwerke | Process for the production of steel with increased ductility |
US3992196A (en) * | 1971-06-25 | 1976-11-16 | Nippon Kokan Kabushiki Kaisha | Method and apparatus for the continuous refining of iron and alloys |
US4067730A (en) * | 1974-04-20 | 1978-01-10 | Thyssen Niederrhein Ag Hutten-Und Walzwerke | Process for the production of steel with increased ductility |
US4194902A (en) * | 1977-09-15 | 1980-03-25 | Skw Trostberg Aktiengesellschaft | Desulfurization agent for ferrous melts and method of using the same |
US4321088A (en) * | 1978-05-11 | 1982-03-23 | Basf Aktiengesellschaft | Process for treating pig iron melts and steel melts or alloys |
US4323392A (en) * | 1979-05-14 | 1982-04-06 | Albert Braun | Agent for desulfurizing crude iron and steel melts, and process for making it |
US4358312A (en) * | 1979-12-29 | 1982-11-09 | Hoechst Aktiengesellschaft | Desulfurizing agent and process for its manufacture |
US4368071A (en) * | 1979-12-29 | 1983-01-11 | Hoechst Aktiengesellschaft | Process for the manufacture of desulfurizing agents for crude iron or steel melts |
US4395282A (en) * | 1981-03-24 | 1983-07-26 | Hoechst Aktiengesellschaft | Desulfurization mixture and process for making it |
US4409028A (en) * | 1979-10-24 | 1983-10-11 | Moore William H | Process for producing cast iron |
US4420333A (en) * | 1980-05-10 | 1983-12-13 | Nippon Carbide Kogyo Kabushiki Kaisha | Powdery desulfurizer composition |
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 |
US4490172A (en) * | 1979-06-29 | 1984-12-25 | Moore William H | Method of melting and refining steel and other ferrous alloys |
US4764211A (en) * | 1985-12-17 | 1988-08-16 | Thyssen Stahl Ag | Fine-grained agent for desulfurizing molten iron |
AU586116B2 (en) * | 1987-02-13 | 1989-06-29 | Cyanamid Canada Inc. | Method of desulfurizing iron |
US5279639A (en) * | 1990-04-06 | 1994-01-18 | Tam Ceramics, Inc. | Compositions for synthesizing ladle slags |
US5343491A (en) * | 1991-11-28 | 1994-08-30 | Carbagas And Von Roll Ag | Method of suppressing dust and fumes during electric steel production |
US5358550A (en) * | 1992-10-26 | 1994-10-25 | Rossborough Manufacturing Company | Desulfurization agent |
EP1146130A2 (en) * | 2000-04-10 | 2001-10-17 | Rossbourugh Manufacturing Co., L.P. | Magnesium injection agent and process for ferrous metal treatment |
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 |
US20040083851A1 (en) * | 2002-10-30 | 2004-05-06 | Rossborough Manufacturing Company, A Delaware Corporation | Reclaimed magnesium desulfurization agent |
US20080196548A1 (en) * | 2007-02-16 | 2008-08-21 | Magnesium Technologies Corporation | Desulfurization puck |
US7731778B2 (en) | 2006-03-27 | 2010-06-08 | Magnesium Technologies Corporation | Scrap bale for steel making process |
US9187792B2 (en) | 2011-01-15 | 2015-11-17 | Alamamet GmbH | Agent for treating molten metals, method for the production and use thereof |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2252795C3 (de) * | 1972-10-27 | 1982-09-09 | Skw Trostberg Ag, 8223 Trostberg | Entschwefelungsmittel für Roheisen- und Ferrolegierungsschmelzen |
DE2252796C3 (de) * | 1972-10-27 | 1982-08-12 | Skw Trostberg Ag, 8223 Trostberg | Entschwefelungsmittel für Roheisen und Ferrolegierungsschmelzen |
FR2432550A1 (fr) * | 1978-08-04 | 1980-02-29 | Sueddeutsche Kalkstickstoff | Procede pour la fabrication d'un melange de desulfuration pulverulent facilement fluidifiable |
JPS55110712A (en) * | 1979-02-15 | 1980-08-26 | Kawasaki Steel Corp | Desulfurizing agent for blowing-in |
DE3022752A1 (de) * | 1980-06-18 | 1982-01-14 | Skw Trostberg Ag, 8223 Trostberg | Entschwefelungsmittel |
DE4242328C2 (de) * | 1992-12-15 | 1995-06-08 | Alfred Dipl Ing Dr Freissmuth | Mittel zur Entschwefelung, Entphosphorung, Entsilicierung und Entstickung von Roheisen- und Gußeisenschmelzen |
DE102011008690A1 (de) | 2011-01-15 | 2012-07-19 | Mechthilde Döring-Freißmuth | Mittel zur Behandlung von Metallschmelzen und Verwendung desselben |
DE102011008691A1 (de) | 2011-01-15 | 2012-07-19 | Mechthilde Döring-Freißmuth | Mittel zur Behandlung von Metallschmelzen, Verfahren zur Herstellung und Verwendung desselben |
-
1968
- 1968-04-29 DE DE19681758250 patent/DE1758250B1/de active Pending
-
1969
- 1969-03-11 SE SE03300/69A patent/SE341196B/xx unknown
- 1969-03-12 CH CH375969A patent/CH514677A/de not_active IP Right Cessation
- 1969-03-12 AT AT243369A patent/AT297768B/de not_active IP Right Cessation
- 1969-03-27 FR FR6909166A patent/FR2007154A1/fr active Pending
- 1969-03-27 BE BE730577D patent/BE730577A/xx not_active IP Right Cessation
- 1969-04-18 LU LU58448D patent/LU58448A1/xx unknown
- 1969-04-28 US US819997A patent/US3598573A/en not_active Expired - Lifetime
- 1969-04-29 GB GB1226088D patent/GB1226088A/en not_active Expired
Cited By (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3716352A (en) * | 1969-10-24 | 1973-02-13 | Kawasaki Steel Co | Sintered desulfurizer for off-furnace use |
US3992196A (en) * | 1971-06-25 | 1976-11-16 | Nippon Kokan Kabushiki Kaisha | Method and apparatus for the continuous refining of iron and alloys |
US3885957A (en) * | 1972-03-01 | 1975-05-27 | Thyssen Niederrhein Ag | Method for the desulfurization of a steel melt |
US3884679A (en) * | 1973-05-24 | 1975-05-20 | Sueddeutsche Kalkstickstoff | Method of preparing a stable mixture of calcium with a compound yielding water at elevated temperature |
US3954446A (en) * | 1974-02-23 | 1976-05-04 | Kubota Ltd. | Method of producing high duty cast iron |
US3955966A (en) * | 1974-03-06 | 1976-05-11 | August Thyssen-Hutte Ag | Method for dispensing a fluidizable solid from a pressure vessel |
US3992195A (en) * | 1974-04-20 | 1976-11-16 | Thyssen Niederrhein Ag Hutten- Und Walzwerke | Process for the production of steel with increased ductility |
US4067730A (en) * | 1974-04-20 | 1978-01-10 | Thyssen Niederrhein Ag Hutten-Und Walzwerke | Process for the production of steel with increased ductility |
US4194902A (en) * | 1977-09-15 | 1980-03-25 | Skw Trostberg Aktiengesellschaft | Desulfurization agent for ferrous melts and method of using the same |
US4321088A (en) * | 1978-05-11 | 1982-03-23 | Basf Aktiengesellschaft | Process for treating pig iron melts and steel melts or alloys |
US4323392A (en) * | 1979-05-14 | 1982-04-06 | Albert Braun | Agent for desulfurizing crude iron and steel melts, and process for making it |
US4490172A (en) * | 1979-06-29 | 1984-12-25 | Moore William H | Method of melting and refining steel and other ferrous alloys |
US4409028A (en) * | 1979-10-24 | 1983-10-11 | Moore William H | Process for producing cast iron |
US4358312A (en) * | 1979-12-29 | 1982-11-09 | Hoechst Aktiengesellschaft | Desulfurizing agent and process for its manufacture |
US4368071A (en) * | 1979-12-29 | 1983-01-11 | Hoechst Aktiengesellschaft | Process for the manufacture of desulfurizing agents for crude iron or steel melts |
US4420333A (en) * | 1980-05-10 | 1983-12-13 | Nippon Carbide Kogyo Kabushiki Kaisha | Powdery desulfurizer composition |
US4395282A (en) * | 1981-03-24 | 1983-07-26 | Hoechst Aktiengesellschaft | Desulfurization mixture and process for making it |
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 |
US4764211A (en) * | 1985-12-17 | 1988-08-16 | Thyssen Stahl Ag | Fine-grained agent for desulfurizing molten iron |
US4832739A (en) * | 1985-12-17 | 1989-05-23 | Thyssen Stahl Ag | Process for desulfurizing molten iron |
AU586116B2 (en) * | 1987-02-13 | 1989-06-29 | Cyanamid Canada Inc. | Method of desulfurizing iron |
US5279639A (en) * | 1990-04-06 | 1994-01-18 | Tam Ceramics, Inc. | Compositions for synthesizing ladle slags |
US5343491A (en) * | 1991-11-28 | 1994-08-30 | Carbagas And Von Roll Ag | Method of suppressing dust and fumes during electric steel production |
US5358550A (en) * | 1992-10-26 | 1994-10-25 | Rossborough Manufacturing Company | Desulfurization agent |
US6395058B2 (en) | 2000-04-10 | 2002-05-28 | Rossborough Manufacturing Co. L.P. | Method of alloying ferrous material with magnesium injection agent |
US6352570B1 (en) | 2000-04-10 | 2002-03-05 | Rossborough Manufacturing Co., Lp | Magnesium desulfurization agent |
US6383249B2 (en) | 2000-04-10 | 2002-05-07 | Rossborough Manufacturing Co. Lp | Magnesium desulfurization agent |
EP1146130A2 (en) * | 2000-04-10 | 2001-10-17 | Rossbourugh Manufacturing Co., L.P. | Magnesium injection agent and process for ferrous metal treatment |
EP1146130B1 (en) * | 2000-04-10 | 2007-05-30 | Magnesium Technologies Corporation | Magnesium injection agent and process for ferrous metal treatment |
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 |
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 |
US9187792B2 (en) | 2011-01-15 | 2015-11-17 | Alamamet GmbH | Agent for treating molten metals, method for the production and use thereof |
Also Published As
Publication number | Publication date |
---|---|
FR2007154A1 (xx) | 1970-01-02 |
CH514677A (de) | 1971-10-31 |
SE341196B (xx) | 1971-12-20 |
BE730577A (xx) | 1969-09-01 |
GB1226088A (xx) | 1971-03-24 |
AT297768B (de) | 1972-04-10 |
LU58448A1 (xx) | 1969-07-21 |
DE1758250B1 (de) | 1971-10-28 |
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