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EP0627012A1 - Procede de desulfuration de bains de fer en fusion avec production minimale de laitier et dispositif approprie pour ce procede. - Google Patents

Procede de desulfuration de bains de fer en fusion avec production minimale de laitier et dispositif approprie pour ce procede.

Info

Publication number
EP0627012A1
EP0627012A1 EP93903828A EP93903828A EP0627012A1 EP 0627012 A1 EP0627012 A1 EP 0627012A1 EP 93903828 A EP93903828 A EP 93903828A EP 93903828 A EP93903828 A EP 93903828A EP 0627012 A1 EP0627012 A1 EP 0627012A1
Authority
EP
European Patent Office
Prior art keywords
slag
weight
max
iron
mgo
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.)
Granted
Application number
EP93903828A
Other languages
German (de)
English (en)
Other versions
EP0627012B1 (fr
Inventor
Anton More
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of EP0627012A1 publication Critical patent/EP0627012A1/fr
Application granted granted Critical
Publication of EP0627012B1 publication Critical patent/EP0627012B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • 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

Definitions

  • the invention relates to a process for the desulfurization of molten iron with minimal slag accumulation and a device suitable therefor.
  • Pig iron as it comes from the blast furnace, usually contains 0.03% - 0.08% sulfur. It is state of the art to reduce the sulfur content of the pig iron before further processing in the steel plant, depending on the intended use of the steel produced, by means of various desulfurization processes to contents of less than 0.01% or less than 0.005%.
  • Unreacted carbide can also be present in the desulfurization slags that are used, which releases toxic and explosive acytylene gas when exposed to water.
  • the object of the invention was to provide a method for desulfurizing iron melts which avoids the disadvantages mentioned, and to provide an apparatus for carrying out the method.
  • a process for the desulphurization of molten iron has been found, which can be used for pig iron as well as cast iron, and which does not have the serious disadvantages of the usual desulphurization processes for molten iron, since almost no sulfur-containing slag is produced from the outset and this can also be desulphurized.
  • Another advantage of the process according to the invention is that there is also no need for expensive processing of a high iron-containing slag.
  • the process according to the invention can do without the expensive desulphurization agents based on carbide or magnesium, which makes it considerably cheaper than the processes currently used which correspond to the prior art.
  • the pig iron is not desulfurized in the torpedo pan or charging pan of the steelworks, as is customary, but instead it is e.g. a specially developed downhole furnace electrically heated by means of graphite or coal electrodes or a correspondingly adapted ladle furnace or electric furnace was used. Resistance heating in this furnace melts such large quantities of basic slag that a weight ratio of iron melt to slag of less than 10, preferably less than 5, and particularly preferably less than 2.5 in the case of continuous desulfurization, is maintained in the desulfurization process.
  • the downhole furnace according to the invention can be tilted and has a pouring device which allows the desulfurized iron melt to be drawn off under the desulfurization slag. This is preferably achieved by means of a pouring pipe, which extends down to the bottom of the working space of the furnace. Opposite the pouring pipe there is an inlet channel for the pig iron to be desulfurized. On Bo 'to the furnace boiler below the intake chute for the pig iron can be mounted a nozzle or a porous plug. However, several nozzles or flushing stones can also be placed on the bottom or on the side walls of the invention. downhole furnace according to the invention.
  • the furnace is expediently lined with crushed coal, charcoal stones or, in particular, on the furnace floor and wherever predominantly liquid iron comes into contact with the lining with carbon-containing, basic or high-alumina refractory stones.
  • melting units can also be used for the process according to the invention.
  • the prerequisite for this is that there is the possibility of melting slag by means of electrodes and pouring the iron either continuously or discontinuously separately from the slag.
  • Melting units which can be used for the methods according to the invention after appropriate adaptation are ladle furnaces or e.g. Electric furnace with an eccentric bottom cut.
  • the refractory lining described is also expedient for ladle ovens or electric ovens which have been adapted for the method according to the invention.
  • the desulfurization process can be carried out by first melting a basic slag in the furnace and then pouring in the sulfur-rich pig iron.
  • the reverse order, especially when using a pan oven, is also possible and useful.
  • the chemical analysis of the slag used is as follows:
  • the preferred composition of the slag has the following chemical analysis:
  • composition of the slag according to the invention has the following chemical composition:
  • the electrodes are immersed in the liquid slag, which is then heated by resistance heating. The remaining quantities of the required slag are dissolved in the slag bath thus formed.
  • the liquid slag is brought to a temperature of 1400-1800 ° C, preferably 1500-1700 ° C, particularly preferably 1550-1650 ° C.
  • the sulfur-containing iron melt is then allowed to flow evenly into this hot slag.
  • the iron melt is desulfurized very quickly.
  • the desulfurization reaction takes place particularly quickly when, for example, a gas consisting of argon, nitrogen or air or mixtures of these gases is blown through a sink or one or more floor nozzles, as a result of which hot slag is flushed against the inflowing iron melt.
  • an iron melt which has already settled on the furnace floor, is stirred vigorously. It can give off the remaining sulfur to the hot slag.
  • the reaction of the iron melt with the slag can be intensified by a funnel in the inlet which is covered by the liquid slag and into which the sulfur-containing iron melt runs. To do this, hot slag is pumped up through the funnel using a gas jet. The hot slag is swirled with the incoming molten iron. It transports the molten iron out of the funnel at the top.
  • Gases such as air and / or water vapor can also be blown into the slag melt or through the slag melt into the iron melt by means of one or more lances immersed in the slag melt from above, thereby accelerating the desulfurization process.
  • the usual desulfurization agents for pig iron for example based on carbide or lime, can also be blown in with the gas through the floor nozzle.
  • Such a measure can be expedient, for example, if an iron melt with a particularly high sulfur content and / or to an extremely low final content has to be desulfurized in the shortest possible time.
  • blowing in a small amount of the desulfurizing agent can also be useful. This is especially true when some blast furnace slag runs with the pig iron in the downhole furnace.
  • a mode of operation is also possible in which the pig iron is poured into the downhole furnace and the desulphurization takes place at the same time. Then desulphurization is carried out and then the pig iron is poured out by tilting the low shaft furnace. If the pouring hole has become blocked, it must be burned up by means of an electrode, for example.
  • the use of a correspondingly adapted ladle furnace or electric furnace is also possible for the method according to the invention.
  • the ladle When using a ladle furnace, the ladle is first filled with pig iron rich in sulfur, and then with the help of electrodes, such a quantity of liquid slag is smelted on the raw iron that the weight ratio of iron to slag does not fall below 10 to 1. Even during the melting of the slag until the end of the desulfurization process, the pig iron is stirred by blowing gases through one or more sink stones at the bottom of the pan.
  • the slag After the slag has melted, it is blown into the melt by means of one or more water-cooled lan air or air and water or water vapor immersed in the slag.
  • the desulphurized pig iron is then poured out through a slide located on the bottom of the pan. Fresh, sulfur-rich pig iron is then poured into the pan and the next batch is desulphurized.
  • the slag is usually exhausted when its sulfur content has exceeded about 6-8% by weight.
  • 750 t to 1000 t of pig iron can be desulfurized from an initial sulfur content of 0.05% to a final sulfur content of 0.01% with a low-chimney furnace containing 5 t of desulphurization slag.
  • a blast furnace that produces 10,000 t of pig iron per day, this is the case after approx. 1 1/2 to 2 1/2 hours.
  • a sulfur breakdown of approximately 1% by weight per hour can be achieved in the slag.
  • a downhole furnace according to the invention which contains 20 t of slag with a composition according to the invention, about 500 t of pig iron per hour can be desulfurized from 0.05 to 0.01% for days.
  • a slag with a high sulfur content which is treated with an oxidizing agent, not only loses its ability to desulphurize, but on the contrary has a sulfurizing effect on molten iron with a low sulfur content.
  • the slag loses part of its sulfur content.
  • the slag When the desulfurization slag has been saturated with sulfur, i.e. if the desired level of desulfurization is no longer achieved, the slag can be subjected to a regeneration process. For this purpose, the pig iron inflow is first stopped and the pig iron is poured out completely.
  • the subsequent regeneration of the slag is carried out by oxidation, if appropriate after adding SiO 2 and / or A1 2 O 3 .
  • the slag can be oxidized by blowing in air and / or oxygen or by adding an oxidizing agent such as iron oxide, iron ore and / or manganese ore.
  • the sulfur content of the oxidized melt can be reduced, for example, from 6% to below 0.20% within a few minutes.
  • a reducing agent for example coal, coke, lignite coke, peat coke or charcoal
  • reducing agent for example coal, coke, lignite coke, peat coke or charcoal
  • Other reducing agents such as Aluminum can be used to reduce the slag's heavy metal oxides.
  • the desulfurization process for pig iron can be started again.
  • the oxidation process produces S0, which can be converted to gypsum, for example, in a conventional scrubber by reacting with hydrated lime in the flue gas of the furnace. This gypsum from the conversion of the flue gases with lime can easily be processed or deposited.
  • the method according to the invention is therefore very environmentally friendly.
  • only a fraction of the desulfurization slag used is obtained, and even this can be processed into high-quality, sulfur-free desulfurization slag.
  • small amounts of gypsum are produced, which can be landfilled or processed without any problems.
  • a small amount of slag is unavoidable because the pig iron containing sulfur cannot be separated quantitatively from the blast furnace slag that is running along before the desulfurization process.
  • small amounts especially of lime, fluorspar and possibly alumina, must be added to the desulfurization slag according to the amount and chemical analysis of the blast furnace slag.
  • Another advantage of the process according to the invention is that the pig iron is heated up during the desulfurization process.
  • the downhole furnace according to the invention can even be used for the additional melting and desulfurization of scrap iron. This can e.g. proceed in such a way that a certain amount of cut iron scrap is continuously charged in the furnace according to the invention.
  • An advantage of the desulphurization process according to the invention that cannot be overlooked is that the described low shaft furnace can be inserted between the blast furnace and converter at various points in the production process without any problems, since, due to its special design principle, between the inlet channel for the sulfur-containing and the pouring hole for the desulfurized pig iron requires very little height.
  • the downhole furnace is electrically heated by means of graphite electrodes 1. It is tiltable and has a pouring spout 2 which extends to the bottom of the working space of the furnace.
  • the pouring pipe enables the desulfurized iron melt 3 to be drawn off under the desulfurization slag 4. Opposite the pouring pipe there is an inlet channel 5 for the pig iron to be desulfurized. At the bottom of the Ofenkess ⁇ lr-, below the gutter for the pig iron, there is a Du. ? 6 attached.
  • a test furnace with an elliptical furnace boiler was used, which was lined with crushed coal and a capacity of 400 mm in length, 260 mm in width and 240 mm deep.
  • the furnace On the pouring side, the furnace had a graphite tube with 100 mm outer diameter and 30 mm inner diameter, which reached down to the bottom of the melting chamber. 20 kg of desulfurization slag were melted in this vessel with the aid of 2 electrodes with a diameter of 100 mm.
  • the slag and cast iron were kept at temperature for half an hour.
  • either slag and melt were stirred with a graphite rod for 5 minutes at the end of the half-hour test time (Examples 1 and 4) or air or air plus water vapor was blown into the slag during the half hour melting time (Examples 2 and 3).
  • the blowing rate of the gases was chosen so that the slag was agitated vigorously, but without large quantities of slag spraying out of the test furnace.
  • the desulfurized cast iron was then poured off through the graphite tube.
  • the cast iron used for the tests contained 0.21% by weight of S, 3.17% by weight of C, 2.06% by weight of Si and 0.27% by weight of Mn.
  • the test results are summarized in Table 1 at the end of the description.
  • the calculated sulfur contents of the slags (S calculated) are also given.
  • the calculated sulfur contents of the slags result from the initial content of the respective slags, i.e. from the sulfur content found in the previous test plus the calculated increase in the S content from the desulfurization of the cast iron during the test.
  • Sample No. 0 indicates the S content of the cast iron used.
  • the sulfur values of the desulfurized cast iron were between 0.010 and 0.017% by weight (Pr.No. 1-3).
  • the calculated sulfur losses of the slags were 0.38% by weight based on the test period of half an hour.
  • the S content of the slag could be reduced to 0.13% by weight by adding 40% manganese ore. (Pr.No. 5).
  • Example 3 compressed air and water vapor were blown into the slag using a lance.
  • the sulfur content of the desulfurized cast iron was between 0.002 and 0.003% by weight (Pr.No. 1-3).
  • the calculated S losses of the slags fluctuated between 0.49 and 0.56% by weight (Pr No. 2-3) based on the test duration of half an hour.
  • the slag temperature was 1530 ° C.
  • the desulfurization effect of the slag was not satisfactory.
  • the S content of the cast iron after the desulfurization process was between 0.044 and 0.059% by weight. (Pr No. 1-4)
  • the slag temperature was 1630 ° C.

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)
  • Vertical, Hearth, Or Arc Furnaces (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé de désulfuration de bains de fonte de fer avec production minimale de laitier et un dispositif convenant pour la mise en oeuvre de ce procédé. Le procédé est caractérisé en ce qu'un laitier présentant la composition (I) ainsi que des impuretés dont la teneur est fonction des matières premières, est amené à une température de 1400-1800 °C, par chauffage par résistance du laitier, au moyen d'électrodes plongeant dans ce laitier, dans un bas-fourneau basculant ou dans un four électrique ou un four à poche de coulée adapté au procédé selon l'invention, après quoi, avec ce laitier, le bain de fonte de fer sulfuré est désulfuré et déversé, soit en discontinu, soit en continu, au-dessous du laitier de désulfuration, le rapport du bain de fonte de fer au laitier ne devant pas être supérieur à 10 : 1 parties en poids, et le laitier de désulfuration étant régénéré en continu et/ou en discontinu.
EP93903828A 1992-02-27 1993-02-25 Procede de desulfuration de bains de fer en fusion avec production minimale de laitier et dispositif approprie pour ce procede Expired - Lifetime EP0627012B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4206091A DE4206091C2 (de) 1992-02-27 1992-02-27 Verfahren zur Entschwefelung von Eisenschmelzen bei minimalem Schlacke-Anfall und eine dafür geeignete Vorrichtung
DE4206091 1992-02-27
PCT/DE1993/000165 WO1993017131A1 (fr) 1992-02-27 1993-02-25 Procede de desulfuration de bains de fer en fusion avec production minimale de laitier et dispositif approprie pour ce procede

Publications (2)

Publication Number Publication Date
EP0627012A1 true EP0627012A1 (fr) 1994-12-07
EP0627012B1 EP0627012B1 (fr) 1997-07-30

Family

ID=6452754

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93903828A Expired - Lifetime EP0627012B1 (fr) 1992-02-27 1993-02-25 Procede de desulfuration de bains de fer en fusion avec production minimale de laitier et dispositif approprie pour ce procede

Country Status (8)

Country Link
US (1) US5466275A (fr)
EP (1) EP0627012B1 (fr)
JP (1) JP3902223B2 (fr)
KR (1) KR100269897B1 (fr)
AT (1) ATE156196T1 (fr)
CA (1) CA2130996A1 (fr)
DE (2) DE4206091C2 (fr)
WO (1) WO1993017131A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8235576B2 (en) 2005-02-23 2012-08-07 Air Liquide Industrial U.S. Lp Concrete cooling injection unit and method of injecting a coolant into a concrete mixture
WO2017084912A1 (fr) * 2015-11-19 2017-05-26 Sms Group Gmbh Procédé et dispositif de nettoyage de scories

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DE19546738C2 (de) * 1995-12-14 1997-12-18 Eko Stahl Gmbh Verfahren zur Entschwefelung von Roheisenschmelzen
DE19609606A1 (de) * 1996-03-12 1997-09-18 Dillinger Huettenwerke Ag Verfahren zum Entschwefeln von Roheisen
AT407260B (de) 1998-05-20 2001-02-26 Voest Alpine Ind Anlagen Verfahren zum herstellen von stahlschmelzen
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
FI122348B (fi) 2008-05-30 2011-12-15 Rautaruukki Oyj Menetelmä kalsiumkarbonaatin tuottamiseksi jäte- ja sivutuotteista
DE102013113197A1 (de) * 2013-11-28 2015-05-28 Voestalpine Stahl Gmbh Verfahren zum Bearbeiten von Entschwefelungsschlacke
RU2588915C1 (ru) * 2015-03-23 2016-07-10 Общество С Ограниченной Ответственностью Ооо "Экос" Способ десульфурации чугуна
JP6263144B2 (ja) * 2015-03-23 2018-01-17 日新製鋼株式会社 製鋼スラグからカルシウムを含有する固体成分を回収する方法、および回収された固体成分
CN105021776B (zh) * 2015-07-28 2017-06-27 西安交通大学 一种生物质锅炉硅酸盐结渣趋势的判定方法
CN107447156B (zh) * 2017-08-01 2019-06-04 江油市长祥特殊钢制造有限公司 热作模具钢及其生产方法
CN113621865B (zh) * 2020-05-06 2022-06-28 宝山钢铁股份有限公司 一种冶炼极细金刚砂线用钢的工艺方法

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DE3535280A1 (de) * 1985-10-03 1987-04-09 Hoechst Ag Entschwefelungsgemisch fuer metallschmelzen, ein verfahren zu seiner herstellung und seine verwendung
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8235576B2 (en) 2005-02-23 2012-08-07 Air Liquide Industrial U.S. Lp Concrete cooling injection unit and method of injecting a coolant into a concrete mixture
WO2017084912A1 (fr) * 2015-11-19 2017-05-26 Sms Group Gmbh Procédé et dispositif de nettoyage de scories

Also Published As

Publication number Publication date
DE59307023D1 (de) 1997-09-04
JPH07504230A (ja) 1995-05-11
EP0627012B1 (fr) 1997-07-30
JP3902223B2 (ja) 2007-04-04
DE4206091C2 (de) 1994-09-22
KR100269897B1 (ko) 2000-10-16
US5466275A (en) 1995-11-14
ATE156196T1 (de) 1997-08-15
KR950700427A (ko) 1995-01-16
DE4206091A1 (de) 1993-09-02
WO1993017131A1 (fr) 1993-09-02
CA2130996A1 (fr) 1993-08-28

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