EP0226994B1 - Mittel zur Entschwefelung von geschmolzenem Eisen sowie Verfahren zur Herstellung des Mittels - Google Patents

Mittel zur Entschwefelung von geschmolzenem Eisen sowie Verfahren zur Herstellung des Mittels Download PDF

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Publication number
EP0226994B1
EP0226994B1 EP86117417A EP86117417A EP0226994B1 EP 0226994 B1 EP0226994 B1 EP 0226994B1 EP 86117417 A EP86117417 A EP 86117417A EP 86117417 A EP86117417 A EP 86117417A EP 0226994 B1 EP0226994 B1 EP 0226994B1
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EP
European Patent Office
Prior art keywords
coal
agent according
agent
gas
calcium carbide
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
EP86117417A
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German (de)
English (en)
French (fr)
Other versions
EP0226994A1 (de
Inventor
Walter Meichsner
Werner Dr. Gmöhling
Manfred Tutte
Karl-Heinz Dr. Peters
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.)
Thyssen Stahl AG
Evonik Operations GmbH
Original Assignee
SKW Trostberg AG
Thyssen Stahl AG
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
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Priority claimed from DE19853544562 external-priority patent/DE3544562C2/de
Priority claimed from DE3544563A external-priority patent/DE3544563C2/de
Application filed by SKW Trostberg AG, Thyssen Stahl AG filed Critical SKW Trostberg AG
Priority to AT86117417T priority Critical patent/ATE54673T1/de
Publication of EP0226994A1 publication Critical patent/EP0226994A1/de
Application granted granted Critical
Publication of EP0226994B1 publication Critical patent/EP0226994B1/de
Anticipated expiration legal-status Critical
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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

  • the invention relates to agents, processes for producing the agent and application of the agent for the desulfurization of molten iron outside the blast furnace.
  • iron smelting means pig iron and cast iron melting.
  • a preferred agent is a mixture consisting of 20 to 90% by weight technical calcium carbide and calcium carbonate, preferably in precipitated form and 2 to 20% by weight carbon distributed therein, the finely divided calcium carbonate / carbon mixture being known under the name diamide lime ( DE-PS 17 58 250).
  • US Pat. No. 3,998,625 describes a desulfurization agent consisting of a combination of lime and other constituents with magnesium
  • US Pat. No. 4,266,969 recommends the use of lime with carbon-containing material and a non-oxidizing conveying gas.
  • a disadvantage of the known agents is the large amounts of slag which, particularly in the torpedo pans but also in the open pans, lead to undesirable deposits and incrustations and also include considerable amounts of iron, which leads to considerable iron losses.
  • a fine-grained desulfurization agent for iron melts which consists of a combination of calcium carbide, at least one substance which releases hydrogen at the temperature of the iron melt and magnesium, the hydrogen-releasing substance according to the preferred embodiments of a solid or liquid hydrocarbon, such as Polyethylene or polypropylene.
  • This means can include additional coal, e.g. Brown or gas coal or anthracite included.
  • the task was therefore to develop a further desulphurization agent based on calcium carbide, which on the one hand does not introduce any further slag-forming constituents into the iron melt and on the other hand develops a gas quantity which is sufficient for the dispersion of the calcium carbide immediately after entering the iron melt and with favorable consumption values and short treatment times achieved low final sulfur levels.
  • This object was achieved by a fine-grained agent which is blown into the molten iron in fluidized form by means of a gas which consists of a mixture of technical calcium carbide and a dried coal which contains at least 15% by weight of volatile constituents and immediately after entering the iron melt releases a gas volume of at least 80 NL gas / kg coal.
  • Technical calcium carbide is understood to mean a commercially available product which contains 65 to 85% by weight of CaC 2 and the rest of which consists predominantly of lime.
  • the proportion of technical calcium carbide can vary within wide limits in the agent according to the invention. The contents of the remaining components fluctuate accordingly.
  • a desulfurization agent is preferably used which contains 50 to 98% by weight calcium carbide and 50 to 2% by weight coal.
  • the agent particularly preferably contains 80 to 96% by weight of calcium carbide and 20 to 4% by weight of coal.
  • the desulfurization agent according to the invention can additionally contain magnesium. Mixtures with contents of 47.5 to 95.5% by weight of technical calcium carbide, 50 to 2% by weight of dried coal and 2 to 40% by weight of magnesium are preferred.
  • a coal type is preferably selected as the carbon component, which as the dried product is pneumatically introduced into the molten iron, ie at a heating rate of 10 3 to 10 60 C / sec. releases about 90% by weight of the volatile constituents within less than 60 seconds, preferably less than 40 seconds.
  • the higher the level of volatiles in the coal the higher the effectiveness of the desulfurization agent.
  • Coals containing at least 25% by weight of volatile constituents are therefore particularly preferably used.
  • Coals are preferably used which develop a gas volume of at least 150 NL / kg in the dried form immediately after entering the iron melt. Coals these conditions are, in particular, lignite, flame coal, gas flame coal, gas coal and fat coal (see Table 1).
  • two or more types of coal with high volatile constituents can also be used in the mixture.
  • the moisture content of the dried coal is preferably less than 0.5% by weight in order to prevent acetylene formation by reaction with the calcium carbide.
  • Such degrees of dryness are achieved in commercially available drying devices such as swirl flow driers, entrained flow driers or grinding driers and when drying in a vacuum in simple units, in which the material to be dried is merely circulated.
  • the magnesium to be used should have a grain size of less than 1 mm.
  • a magnesium is preferably used which has already been comminuted ⁇ 500 ⁇ m, particularly preferred is a magnesium which has a grain size ⁇ 350 ⁇ m.
  • fluorspar it may prove expedient to add 1 to 10% by weight of fluorspar to the desulfurization mixture, e.g. to favorably influence the properties of the slag produced during the desulfurization treatment.
  • 1 to 10% by weight of fluorspar Preferably 2 to 6% by weight of fluorspar is added to the mixture.
  • fluorspar ball mill dust (waste from aluminum production) consisting of aluminum oxide with proportions of up to 30% by weight aluminum can be added to the agent.
  • the desulfurization agent according to the invention is produced in such a way that the dried coal is metered into the pre-broken or pre-ground calcium carbide and the mixture is ground in a mill to the desired degree of fineness. It can be useful to work under an inert gas blanket in order to remove any small amounts of acetylene from the mixing and grinding plant. You can also grind the carbide and coal separately and mix them together afterwards.
  • the constituents of the agent according to the invention are ground and mixed intensively, these being preferably comminuted to such an extent that at least 90% by weight of the mixture has a grain size ⁇ 200 ⁇ m, but particularly preferably 90% has a grain size ⁇ 100 ⁇ m and 40 to 65 wt .-% have a grain size ⁇ 50 microns. Certain deviations from this are irrelevant to the desulfurization effect.
  • the agent which consists of calcium carbide and dried coal, magnesium is metered in, so that the agent is pneumatically conveyed into the melt as a homogeneous mixture.
  • the technical calcium carbide content is preferably 47.5 to 95.5% by weight, particularly preferably 66 to 86% by weight, of the. on dried coal to 50 to 2% by weight, particularly preferably 20 to 4% by weight and that of fine-grained magnesium to 2.5 to 40% by weight, particularly preferably 10 to 30% by weight.
  • This method of separate fluidization and co-injection of the separately fluidized mixtures (coinjection) has the advantage that the magnesium can also be used in a larger form.
  • the desulfurization agent according to the invention is expediently blown into the molten iron as deeply as possible in fluidized form with a conveying gas amount of 3 to 30 NUkg.
  • the delivery rate of the agent should be 10 to 100 kg / min; preferably a rate of 30 to 80 kg / min of desulfurizing agent is used.
  • Non-oxidizing gases such as argon or nitrogen alone or as a mixture or dried air are preferably used as the conveying gas for the desulfurization agent.
  • the desulfurization agent according to the invention has considerable advantages over previously known agents in connection with the method according to the invention. Apart from the small amount of ash it contains, the coal brings practically no other slag-forming components into the iron melt. This means that considerably less slag is obtained when using the desulfurization agent according to the invention than when using calcium carbonate or calcium hydroxide as gas-releasing additives.
  • the coal Compared to the known hydrogen and carbon dioxide-releasing additives, the coal has the advantage that a sufficient amount of gas develops immediately after entering the molten iron and thus a practically complete dispersion of the finely divided calcium carbide and the magnesium in the molten iron is achieved. As a result, the desulfurization effect of the agent according to the invention is superior to the known desulfurization mixtures based on calcium carbide.
  • the agent according to the invention has the surprising advantage that the treatment times of the iron melts are reduced considerably, and more so than was expected after the reactivity of the magnesium and the calcium carbide.
  • the desulfurization agent according to the invention is just as suitable in connection with the blowing process described for hot metal desulfurization in the open pan as in the torpedo pan.
  • composition of the agent guarantees sufficient distribution so that a high degree of utilization of the desulfurizing agent is achieved.
  • the treatment times of the iron melts are short, so that the melt is only slightly cooled.
  • the amount of slag produced is small, which means that the iron losses when removing the slag are insignificant.
  • Number 10 relates to a known desulfurization agent consisting of 50% by weight of magnesium and 50% by weight of ball mill dust (A1 2 0 2 and Al).
  • Numbers 3, 7 to 9 and 12 and 13 show the results which were obtained in open pans with compositions composed according to the invention.
  • the means according to the invention are superior to the conventional means.
  • the amount of gas split off in 1 / kg is the amount of gas that escapes when the coal is heated to crude iron temperature very quickly.
  • the volatile constituents of the diamide lime are the amount of CO 2 released during carbonate decomposition.
  • the duration of gas evolution indicates the time (sec) in which approximately 90% of the total amount of gas is split off.

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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Cereal-Derived Products (AREA)
EP86117417A 1985-12-17 1986-12-15 Mittel zur Entschwefelung von geschmolzenem Eisen sowie Verfahren zur Herstellung des Mittels Expired - Lifetime EP0226994B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86117417T ATE54673T1 (de) 1985-12-17 1986-12-15 Mittel zur entschwefelung von geschmolzenem eisen sowie verfahren zur herstellung des mittels.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19853544562 DE3544562C2 (de) 1985-12-17 1985-12-17 Feinkörniges Mittel zur Entschwefelung von Eisenschmelzen
DE3544563A DE3544563C2 (de) 1985-12-17 1985-12-17 Mittel zur Entschwefelung von geschmolzenem Eisen
DE3544562 1985-12-17
DE3544563 1985-12-17

Publications (2)

Publication Number Publication Date
EP0226994A1 EP0226994A1 (de) 1987-07-01
EP0226994B1 true EP0226994B1 (de) 1990-07-18

Family

ID=25838925

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86117417A Expired - Lifetime EP0226994B1 (de) 1985-12-17 1986-12-15 Mittel zur Entschwefelung von geschmolzenem Eisen sowie Verfahren zur Herstellung des Mittels

Country Status (11)

Country Link
US (2) US4764211A (ja)
EP (1) EP0226994B1 (ja)
JP (1) JPH0645813B2 (ja)
CN (1) CN1006809B (ja)
AU (1) AU571147B2 (ja)
BR (1) BR8606249A (ja)
CA (1) CA1261633A (ja)
DE (1) DE3672779D1 (ja)
ES (1) ES2016557B3 (ja)
FI (1) FI83095C (ja)
NO (1) NO168057C (ja)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011116501A1 (de) 2011-10-20 2013-04-25 Almamet Gmbh Bitumen enthaltendes Entschwefelungsmittel
DE202014100884U1 (de) 2014-02-26 2014-03-13 Almamet Gmbh Schlackekonditionierer für die Entschwefelung in der Sekundärmetallurgie von Stahl

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3734877C1 (de) * 1987-10-15 1988-10-27 Sueddeutsche Kalkstickstoff Mittel und Verfahren zur Aufstickung von Gusseisen
DE3831831C1 (ja) * 1988-09-20 1989-11-02 Skw Trostberg Ag, 8223 Trostberg, De
DE3908071A1 (de) * 1989-03-13 1990-09-20 Hoechst Ag Mittel und verfahren zum entschwefeln von metallschmelzen
US4941914A (en) * 1989-05-18 1990-07-17 Elkem Metals Company Desulfurization agent
US5078784A (en) * 1990-03-14 1992-01-07 Elkem Metals Company Desulfurization agent
US5002733A (en) * 1989-07-26 1991-03-26 American Alloys, Inc. Silicon alloys containing calcium and method of making same
US5149364A (en) * 1990-03-14 1992-09-22 Elkem Metals Company Desulfurization agent
US5021086A (en) * 1990-07-05 1991-06-04 Reactive Metals And Alloys Corporation Iron desulfurization additive and method for introduction into hot metal
DE4128499C2 (de) * 1991-08-28 1994-11-24 Thyssen Stahl Ag Verfahren zur Behandlung von Roheisenschmelzen zu deren Entschwefelung
CA2054244C (en) * 1991-10-25 2000-08-01 Bruce James Barker Powdered desulfurizing reagent and process of use
US5358550A (en) * 1992-10-26 1994-10-25 Rossborough Manufacturing Company Desulfurization agent
DE4242328C2 (de) * 1992-12-15 1995-06-08 Alfred Dipl Ing Dr Freissmuth Mittel zur Entschwefelung, Entphosphorung, Entsilicierung und Entstickung von Roheisen- und Gußeisenschmelzen
ATA115194A (de) * 1994-06-08 1997-07-15 Donau Chemie Ag Entschwefelungsmittel für roheisen- und gusseisenschmelzen
AT406690B (de) * 1994-12-09 2000-07-25 Donau Chemie Ag Mittel zur behandlung von roheisen- und gusseisenschmelzen zum zweck der entschwefelung
US5873924A (en) * 1997-04-07 1999-02-23 Reactive Metals & Alloys Corporation Desulfurizing mix and method for desulfurizing molten iron
US6372014B1 (en) 2000-04-10 2002-04-16 Rossborough Manufacturing Co. L.P. Magnesium injection agent for ferrous metal
US6352570B1 (en) 2000-04-10 2002-03-05 Rossborough Manufacturing Co., Lp Magnesium desulfurization agent
US6770115B2 (en) * 2002-10-18 2004-08-03 Remacor, Inc. Process for magnesium granules
US6989040B2 (en) * 2002-10-30 2006-01-24 Gerald Zebrowski Reclaimed magnesium desulfurization agent
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
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
CN101584696A (zh) 2008-05-21 2009-11-25 上海艾力斯医药科技有限公司 包含喹唑啉衍生物的组合物及制备方法、用途
CN112391510A (zh) * 2020-10-29 2021-02-23 张家港宏昌钢板有限公司 一种新的铁水脱硫工艺

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Publication number Priority date Publication date Assignee Title
DE1758250B1 (de) * 1968-04-29 1971-10-28 Sueddeutsche Kalkstickstoff Mittel zum Entschwefeln von Eisenschmelzen
US4159906A (en) * 1972-10-27 1979-07-03 Suddeutsche Kalkstickstoff-Werke Aktiengesellschaft Method and composition for the desulfurization of molten metals
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
DE2531047B2 (de) * 1975-07-11 1978-07-06 Kloeckner-Werke Ag, 4100 Duisburg Verfahren zum Entschwefeln von Roheisen
US3998625A (en) * 1975-11-12 1976-12-21 Jones & Laughlin Steel Corporation Desulfurization method
DE2741588C2 (de) * 1977-09-15 1985-02-07 Skw Trostberg Ag, 8223 Trostberg Mittel zum Entschwefeln von Eisenschmelzen
FR2432550A1 (fr) * 1978-08-04 1980-02-29 Sueddeutsche Kalkstickstoff Procede pour la fabrication d'un melange de desulfuration pulverulent facilement fluidifiable
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US4266969A (en) * 1980-01-22 1981-05-12 Jones & Laughlin Steel Corporation Desulfurization process
DE3022752A1 (de) * 1980-06-18 1982-01-14 Skw Trostberg Ag, 8223 Trostberg Entschwefelungsmittel
DE3111510A1 (de) * 1981-03-24 1982-10-07 Hoechst Ag, 6000 Frankfurt Entschwefelungsgemisch und verfahren zu seiner herstellung
CA1240842A (en) * 1984-05-16 1988-08-23 Heinrich Rellermeyer Method, process and composition for desulfurizing pig-iron melts
US4581068A (en) * 1985-05-06 1986-04-08 Frank & Schulte Gmbh Shaped body for feeding cupola furnaces
DE3535280A1 (de) * 1985-10-03 1987-04-09 Hoechst Ag Entschwefelungsgemisch fuer metallschmelzen, ein verfahren zu seiner herstellung und seine verwendung

Non-Patent Citations (1)

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Title
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011116501A1 (de) 2011-10-20 2013-04-25 Almamet Gmbh Bitumen enthaltendes Entschwefelungsmittel
WO2013057262A2 (de) 2011-10-20 2013-04-25 Almamet Gmbh Bitumen enthaltendes entschwefelungsmittel
DE102011116501C5 (de) 2011-10-20 2018-05-24 Almamet Gmbh Bitumen enthaltendes Entschwefelungsmittel
DE202014100884U1 (de) 2014-02-26 2014-03-13 Almamet Gmbh Schlackekonditionierer für die Entschwefelung in der Sekundärmetallurgie von Stahl

Also Published As

Publication number Publication date
ES2016557B3 (es) 1990-11-16
NO168057B (no) 1991-09-30
BR8606249A (pt) 1987-09-29
JPH02163308A (ja) 1990-06-22
NO865074L (no) 1987-06-18
FI83095B (fi) 1991-02-15
CN86108525A (zh) 1987-07-29
CN1006809B (zh) 1990-02-14
NO168057C (no) 1992-01-08
AU6616786A (en) 1987-06-18
CA1261633A (en) 1989-09-26
DE3672779D1 (de) 1990-08-23
FI865126A0 (fi) 1986-12-16
EP0226994A1 (de) 1987-07-01
FI83095C (fi) 1991-05-27
FI865126A (fi) 1987-06-18
AU571147B2 (en) 1988-03-31
US4764211A (en) 1988-08-16
US4832739A (en) 1989-05-23
JPH0645813B2 (ja) 1994-06-15
NO865074D0 (no) 1986-12-16

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Opponent name: PECHINEY

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Opponent name: PECHINEY * 910417 ALMAMET GMBH

Effective date: 19910208

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Opponent name: ALMAMET GMBH

Opponent name: PECHINEY

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