EP0061011B1 - Procédé pour la fabrication d'agents de désulfuration de fonte ou d'acier fondus - Google Patents

Procédé pour la fabrication d'agents de désulfuration de fonte ou d'acier fondus Download PDF

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Publication number
EP0061011B1
EP0061011B1 EP82101427A EP82101427A EP0061011B1 EP 0061011 B1 EP0061011 B1 EP 0061011B1 EP 82101427 A EP82101427 A EP 82101427A EP 82101427 A EP82101427 A EP 82101427A EP 0061011 B1 EP0061011 B1 EP 0061011B1
Authority
EP
European Patent Office
Prior art keywords
mixture
weight
calcium oxide
calcium
cao
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
Application number
EP82101427A
Other languages
German (de)
English (en)
Other versions
EP0061011A1 (fr
Inventor
Albert Braun
Willi Dr. Portz
Georg Dr. Strauss
Hans-Martin Dipl.-Ing. Delhey
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.)
Krupp Stahl AG
Hoechst AG
Original Assignee
Krupp Stahl AG
Hoechst 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
Application filed by Krupp Stahl AG, Hoechst AG filed Critical Krupp Stahl AG
Priority to AT82101427T priority Critical patent/ATE9596T1/de
Publication of EP0061011A1 publication Critical patent/EP0061011A1/fr
Application granted granted Critical
Publication of EP0061011B1 publication Critical patent/EP0061011B1/fr
Expired legal-status Critical Current

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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
    • 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
    • C21C7/064—Dephosphorising; Desulfurising
    • C21C7/0645—Agents used for dephosphorising or desulfurising

Definitions

  • the present invention relates to a process for the production of desulfurization agents based on calcium oxide-containing calcium carbide for pig iron and steel melts, a calcium carbide-calcium oxide melt mixture having a CaO content of 20 to 80% by weight first being produced from lime and coke, which is allowed to solidify into a block by allowing it to cool; then, while the solidified block still has an average temperature of more than 400 ° C., it is broken down to grain sizes of less than 150 mm and calcium oxide is added to the comminuted mixture, which is still at least 400 ° C., in accordance with the CaO content desired in the end product, and the mixture is then ground with vigorous mixing to grain sizes of less than 10 mm.
  • a method is already known from EP-A2-19 086.
  • DE-C3-2 037 758 describes a process for the production of calcium carbide for the desulfurization of molten metals by introducing quicklime (CaO) and fluorspar into molten calcium carbide.
  • the additives are used with a content of adhesive and crystal water less than 5% by weight.
  • the burnt lime can be partially replaced by a gas-releasing substance such as limestone, which increases the porosity of the carbide and thus the active surface offered during the desulfurization.
  • Coke breeze can also be added to the carbide.
  • DE-C3-22 36160 describes an agent for the desulfurization of liquid pig iron based on calcium oxide, the reactive calcium oxide carbon, e.g. B. in the form of carbon black, and may contain calcium carbide.
  • Desulphurization agents based on calcium carbide which contain substances which release water at the temperature of the molten metal, are already known from DE-B2-22 52 795.
  • These agents which are mixtures of commercially available carbide with, for example, Ca (OH) 2 as water-releasing substance and possibly carbon and calcium carbonate, have the disadvantage that they are mixtures produced by mechanical mixing, in which carbide particles are separated apart from Ca (OH) 2 - Particles are present, which leads to a higher consumption, uneven and violent gas reactions and a large spread with regard to the desulfurization effect when using these products, which makes a targeted use of these agents difficult.
  • the older, unpublished EP-A1-31 534 relates to a process for the production of desulfurizing agents with a content of 1-6% by weight of chemically bound water based on calcium oxide-containing calcium carbide for pig iron and steel melts, which is characterized in that that a calcium carbide-calcium oxide melt mixture with a CaO content of 20 to 80% by weight is first produced from lime and coke, which mixture is allowed to solidify into a block by allowing it to cool; that one, while the solidified block still has an average temperature of more than 400 ° C, breaks it down to grain sizes less than 150 mm and gives up on the crushed and still at least 400 ° C hot mixture calcium oxide in such an amount that the resulting mixture resulting total CaO content corresponds to the desired CaO content in the end product, then the mixture with intensive mixing and in the presence of air or nitrogen with a moisture content of 5 to 20 g / m 3 (at 1.013 bar and 273.15 K) Grind temperatures below 100 ° C to grain sizes smaller than 10
  • the end product When mixing with free carbon and carbonate, it is preferred to add such an amount that the end product contains 0.5 to 8% by weight of free carbon and 0.5 to 20% by weight of carbonates of calcium, magnesium or sodium. In addition, the end product preferably contains 1-6% by weight of chemically bound water. The intensive mixing and grinding is best carried out at 10-50 ° C.
  • a calcium carbide-calcium oxide starting melt mixture with a CaO content of 20 to 45% by weight which was obtained in a known manner from lime and coke by thermal means.
  • the process according to the invention and the process of EP-A2-19 086 have the further advantages that a specific Möller composition is not set in each case to produce the carbide melt and the Lime does not have to be finely ground to a certain grain size beforehand, but that a carbide block can be assumed whose C a C 2 : CaO weight ratio can fluctuate within a very wide range, ie can be practically arbitrary, and the lime also in coarse-grained form, for example in a grain size between 8 and 60 mm, can be used.
  • composition according to the invention is that present on the surface of each grain Ca (OH) 2 close to CaC 2, is set very early and uniformly in motion whereby the desulfurizing reaction. With comparable desulfurization results, smaller amounts of the desulfurization agent are required and more targeted results are possible.
  • the block After the block had cooled to an average temperature of about 600 ° C, it was pre-broken to grain sizes smaller than 150 mm and the carbide, which was still 500 ° G hot, was overlaid with so much lime with a grain size of 8 to 60 mm that the resulting mixture contained a total CaO content of 50% by weight.
  • 850 kg of this mixture were mixed with 100 kg limestone (grain size less than 1 mm) and 50 kg of coke breeze (grain size less than 3 mm) and with passage of 1,500 m 3 / h of air with a moisture content of 10 g / m 3 (at 15 ° C) in a rotary mill with a throughput of 500 kg / h at 50 ° C to grain sizes between 0 and 0.1 mm.
  • the product obtained contained 2% by weight of chemically bound water.
  • Calcium carbide is produced thermally from lime and coke in a known manner, the lime-coke mixture in the entire Möller being adjusted to a weight ratio of approximately 110:40, which corresponds to a carbide with a CaO content of approximately 45% by weight.
  • CaO with a grain size of 3-8 mm is added to the tapping jet of this carbide in such an amount that an average content of approx. 80% by weight CaO results in the tapping crucible (approx. .
  • the block is pre-crushed to a grain size of less than 150 mm and as much lime with a grain size of 8 to 60 mm is layered on the hot mixture. That the average CaO content is 90% by weight.
  • 875 kg of this mixture are mixed with 100 kg limestone (grain size less than 1 mm) and 25 kg of coke breeze (grain size less than 3 mm) and with passage of 1,500 m 3 / h of air with a moisture content of 10 g / m 3 (at 15 ° C) in a rotary mill with a throughput of 500 kg / h at 50 ° C to a grain size less than 0.1 mm.
  • the product obtained contains 2.5% by weight of chemically bound water.

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)
  • Treatment Of Steel In Its Molten State (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Claims (4)

1. Procédé de préparation d'agents de désulfuration à base de carbure de calcium contenant de l'oxyde de calcium pour bains de fonte brute et d'acier, dans lequel on prépare d'abord, à partir de chaux et de coke, un mélange fondu carbure de calcium/oxyde de calcium d'une teneur en CaO de 20-80 % en poids, que l'on laisse refroidir et solidifier en un bloc, on concasse ensuite grossièrement dans un premier temps ce bloc solidifié pendant qu'il est encore à une température moyenne de plus de 400 °C, en morceaux de moins de 150 mm et on ajoute au mélange chaud concassé et ayant encore une température d'au moins 400 °C une quantité d'oxyde de calcium correspondant à la teneur en CaO recherchée dans le produit final, et on broie ensuite le mélange avec agitation intense à des dimensions de particules de moins de 10 mm, caractérisé en ce que l'on effectue le mélange intensif et le broyage avec addition de carbone libre et de carbonate en présence d'air ou d'azote d'une teneur en humidité de 5-20 g/m3 (sous 1,013 bar et à 273,15 K) à des températures inférieures à 100°C.
2. Procédé selon la revendication 1, caractérisé en ce que le produit final contient 0,5-8 % en poids de carbone libre et 0,5-20 % en poids de carbonate de calcium, de magnésium ou de sodium.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le produit final contient 1-6 % en poids d'eau liée chimiquement.
4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que l'on effectue l'action de mélange et le broyage à 10-50 °C.
EP82101427A 1981-03-24 1982-02-25 Procédé pour la fabrication d'agents de désulfuration de fonte ou d'acier fondus Expired EP0061011B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82101427T ATE9596T1 (de) 1981-03-24 1982-02-25 Verfahren zur herstellung von entschwefelungsmitteln fuer roheisen- oder stahlschmelzen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19813111509 DE3111509A1 (de) 1981-03-24 1981-03-24 Verfahren zur herstellung von entschwefelungsmitteln fuer roheisen- oder stahlschmelzen
DE3111509 1981-03-24

Publications (2)

Publication Number Publication Date
EP0061011A1 EP0061011A1 (fr) 1982-09-29
EP0061011B1 true EP0061011B1 (fr) 1984-09-26

Family

ID=6128139

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82101427A Expired EP0061011B1 (fr) 1981-03-24 1982-02-25 Procédé pour la fabrication d'agents de désulfuration de fonte ou d'acier fondus

Country Status (10)

Country Link
US (1) US4400292A (fr)
EP (1) EP0061011B1 (fr)
JP (1) JPS57169010A (fr)
AT (1) ATE9596T1 (fr)
BR (1) BR8201618A (fr)
CA (1) CA1184384A (fr)
DD (1) DD202183A5 (fr)
DE (2) DE3111509A1 (fr)
ES (1) ES8302104A1 (fr)
ZA (1) ZA821939B (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3535280A1 (de) * 1985-10-03 1987-04-09 Hoechst Ag Entschwefelungsgemisch fuer metallschmelzen, ein verfahren zu seiner herstellung und seine verwendung

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1408188A1 (de) * 1959-12-19 1968-10-17 Hoesch Ag Verfahren zur Entschwefelung von Roheisenbaedern
AT264560B (de) * 1966-08-25 1968-09-10 Gustav Dipl Ing Wolfram Basisches Stahlherstellungsverfahren
DE2037758C3 (de) * 1970-07-30 1979-08-02 Hoechst Ag, 6000 Frankfurt Verfahren zur Herstellung von CaIciumkarbid zur Entschwefelung von Metallschmelzen
LU63607A1 (fr) * 1971-07-26 1973-02-05
DE2252795C3 (de) * 1972-10-27 1982-09-09 Skw Trostberg Ag, 8223 Trostberg Entschwefelungsmittel für Roheisen- und Ferrolegierungsschmelzen
DE2326539C3 (de) * 1973-05-24 1975-11-13 Sueddeutsche Kalkstickstoff-Werke Ag, 8223 Trostberg Verfahren zur Herstellung eines Entschwefelungsgemisches für Eisenschmelzen aus Calciumcarbid und mindestens einem wasserhaltigen Stoff
IT1047585B (it) * 1975-09-26 1980-10-20 Centro Speriment Metallurg Perfezionamento alla disossidazione e desolforazione dell acciaio
DE2741588C2 (de) * 1977-09-15 1985-02-07 Skw Trostberg Ag, 8223 Trostberg Mittel zum Entschwefeln von Eisenschmelzen
DE2919324A1 (de) * 1979-05-14 1980-12-04 Hoechst Ag Entschweflungsmittel fuer roheisen- und stahlschmelzen sowie ein verfahren zu ihrer herstellung
DE2920353A1 (de) * 1979-05-19 1980-11-27 Hoechst Ag Verfahren zur herstellung von entschweflungsmitteln fuer roheisen- oder stahlschmelzen
DE2952686A1 (de) * 1979-12-29 1981-07-02 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von entschwefelungsmitteln fuer roheisen- oder stahlschmelzen
ES8200147A1 (es) * 1979-12-29 1981-11-01 Hoechst Ag Procedimiento para la preparacion de un agente para la de- sulfuracion de masas fundidas metalicas

Also Published As

Publication number Publication date
BR8201618A (pt) 1983-02-08
DE3260809D1 (en) 1984-10-31
US4400292A (en) 1983-08-23
JPH0135883B2 (fr) 1989-07-27
ATE9596T1 (de) 1984-10-15
ES510769A0 (es) 1983-02-01
ES8302104A1 (es) 1983-02-01
DD202183A5 (de) 1983-08-31
DE3111509A1 (de) 1982-10-07
ZA821939B (en) 1983-02-23
EP0061011A1 (fr) 1982-09-29
CA1184384A (fr) 1985-03-26
JPS57169010A (en) 1982-10-18

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