EP0128131A1 - Procédé pour éliminer le soufre pendant la fusion de fonte brute - Google Patents

Procédé pour éliminer le soufre pendant la fusion de fonte brute Download PDF

Info

Publication number: EP0128131A1
Authority: EP; European Patent Office
Prior art keywords: fluidized bed; coal; lumpy; desulfurizing; slag
Prior art date: 1983-05-04
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

EP84890076A

Other languages

German (de)

English (en)

Other versions

EP0128131B1 (fr

Inventor

Horst Dipl.-Ing. Sulzbacher

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.)

Voestalpine AG

Original Assignee

Voestalpine 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.)

1983-05-04

Filing date

1984-04-26

Publication date

1984-12-12

1984-04-26 Application filed by Voestalpine AG filed Critical Voestalpine AG

1984-12-12 Publication of EP0128131A1 publication Critical patent/EP0128131A1/fr

1987-04-01 Application granted granted Critical

1987-04-01 Publication of EP0128131B1 publication Critical patent/EP0128131B1/fr

Status Expired legal-status Critical Current

Links

NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 19
238000002844 melting Methods 0.000 title claims abstract description 13
230000008018 melting Effects 0.000 title claims abstract description 13
229910000805 Pig iron Inorganic materials 0.000 title claims abstract description 11
238000000034 method Methods 0.000 title claims description 18
239000005864 Sulphur Substances 0.000 title 1
239000003795 chemical substances by application Substances 0.000 claims abstract description 32
239000003245 coal Substances 0.000 claims abstract description 22
239000002893 slag Substances 0.000 claims abstract description 22
230000003009 desulfurizing effect Effects 0.000 claims abstract description 21
229910052717 sulfur Inorganic materials 0.000 claims abstract description 18
239000011593 sulfur Substances 0.000 claims abstract description 18
OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
229910052799 carbon Inorganic materials 0.000 claims abstract description 8
238000006477 desulfuration reaction Methods 0.000 claims description 25
230000023556 desulfurization Effects 0.000 claims description 24
239000000463 material Substances 0.000 claims description 4
FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
229910052749 magnesium Inorganic materials 0.000 claims description 3
239000011777 magnesium Substances 0.000 claims description 3
229910045601 alloy Inorganic materials 0.000 claims description 2
239000000956 alloy Substances 0.000 claims description 2
150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
150000001247 metal acetylides Chemical class 0.000 claims description 2
238000004064 recycling Methods 0.000 claims description 2
OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
239000011575 calcium Substances 0.000 claims 1
229910052791 calcium Inorganic materials 0.000 claims 1
239000008187 granular material Substances 0.000 claims 1
WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
239000000203 mixture Substances 0.000 claims 1
239000002245 particle Substances 0.000 abstract 2
XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
238000006243 chemical reaction Methods 0.000 description 7
ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
239000005997 Calcium carbide Substances 0.000 description 5
235000008733 Citrus aurantifolia Nutrition 0.000 description 5
235000011941 Tilia x europaea Nutrition 0.000 description 5
229910052742 iron Inorganic materials 0.000 description 5
239000004571 lime Substances 0.000 description 5
CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 5
239000007789 gas Substances 0.000 description 4
239000000292 calcium oxide Substances 0.000 description 3
235000012255 calcium oxide Nutrition 0.000 description 3
229910052751 metal Inorganic materials 0.000 description 3
239000002184 metal Substances 0.000 description 3
229910014813 CaC2 Inorganic materials 0.000 description 2
VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
238000003723 Smelting Methods 0.000 description 2
QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
239000007795 chemical reaction product Substances 0.000 description 2
238000010309 melting process Methods 0.000 description 2
229910052760 oxygen Inorganic materials 0.000 description 2
239000001301 oxygen Substances 0.000 description 2
238000011946 reduction process Methods 0.000 description 2
XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
TUEGREKNWIPDRA-UHFFFAOYSA-N [Ca].[Mn] Chemical compound [Ca].[Mn] TUEGREKNWIPDRA-UHFFFAOYSA-N 0.000 description 1
230000002378 acidificating effect Effects 0.000 description 1
230000002776 aggregation Effects 0.000 description 1
238000004220 aggregation Methods 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
229910000019 calcium carbonate Inorganic materials 0.000 description 1
AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
239000000920 calcium hydroxide Substances 0.000 description 1
235000011116 calcium hydroxide Nutrition 0.000 description 1
229910001861 calcium hydroxide Inorganic materials 0.000 description 1
JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
229910052918 calcium silicate Inorganic materials 0.000 description 1
235000012241 calcium silicate Nutrition 0.000 description 1
239000000969 carrier Substances 0.000 description 1
239000010883 coal ash Substances 0.000 description 1
238000004939 coking Methods 0.000 description 1
238000002485 combustion reaction Methods 0.000 description 1
230000006735 deficit Effects 0.000 description 1
230000001419 dependent effect Effects 0.000 description 1
238000004090 dissolution Methods 0.000 description 1
230000000694 effects Effects 0.000 description 1
238000005265 energy consumption Methods 0.000 description 1
230000002349 favourable effect Effects 0.000 description 1
238000002309 gasification Methods 0.000 description 1
239000007788 liquid Substances 0.000 description 1
239000000155 melt Substances 0.000 description 1
150000002739 metals Chemical class 0.000 description 1
YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
229910052683 pyrite Inorganic materials 0.000 description 1
239000011028 pyrite Substances 0.000 description 1
229910052710 silicon Inorganic materials 0.000 description 1
239000010703 silicon Substances 0.000 description 1
239000007787 solid Substances 0.000 description 1
239000000126 substance Substances 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0006—Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state
- C21B13/0013—Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state introduction of iron oxide into a bath of molten iron containing a carbon reductant
- C21B13/002—Reduction of iron ores by passing through a heated column of carbon

Definitions

the invention relates to a method for removing sulfur in the melting of pig iron in a coal fluidized bed.
the invention now aims to avoid such a separate desulfurization of the melt and to carry out most or all of the desulfurization work in the melting reactor.
the invention essentially consists in introducing lumpy and / or granular desulfurizing agent into the fluidized bed of carbon and optionally additionally into the slag layer.
the use of dusty fine lime in the form of hydrated lime or quicklime has proven to be disadvantageous, since dusty fine lime is largely discharged again with the blown-in gas and only a small amount is available for desulfurization in the melting chamber.
the exclusive use of lumpy lime leads to insufficient dissolution in the mostly acidic slag from the coal ash due to the formation of a dicalcium silicate layer on the grain surface.
the desulfurization reaction with CaO is endothermic and preferably takes place in the direction of higher temperatures. If the oxygen activity or the FeO content of the slag is high, then an impairment of the desulfurization efficiency must be expected, above all because the Si content of the molten metal is low.
the feedstocks intended for post-desulfurization are now metered into the meltdown generator in granular and / or lumpy form and whirled together with the coal in accordance with their grain size. They bind the carbon sulfur in a solid, liquid or sublimed state of aggregation or, in the case of coarser grains, immediately fall through the fluidized bed and slowly dissolve in the slag layer in close contact with the melting iron sponge.
the heavy weight of the desulfurization reaction can be shifted into the fluidized bed or into the slag layer by varying the lumpy or granular fraction of the desulfurization agent.
manganese calcium, magnesium, alkalis or rare earths in the form of oxides, carbides, carbonates, alloys, mixed metals or in metallic form can be used as the desulfurizing agent.
the use of calcium carbonate alone has the disadvantage that, when charging directly into the gasifier, not inconsiderable amounts of energy are required for the expulsion and conversion of C0 2 .
Calcium carbide is therefore used according to the invention in a particularly preferred manner as a desulfurization agent. The desulfurization reaction with CaC 2 takes place with the release of energy and preferably in the direction of low temperatures.
Calcium carbide also acts as a deoxidizer to reduce the FeO content in the slag.
the reaction products CaO and CaS are taken up by the slag.
Ladder provides a control option by combined loading of the desulfurization rooms (fluidized bed for coal desulfurization and slag layer for iron desulfurization).
the grain size and quality of the desulfurization agent play an important role here.
Such a control option is advantageously achieved by introducing the proportion of the desulfurizing agent for the coal fluidized bed in the grain size range of 0.5-5 mm and the proportion of the desulfurizing agent for the slag in the grain size range of 5 - 50 mm, these two parts in wide limits can be varied and in this way an adjustment of the heavy weight of the desulfurization reaction to the fluidized bed or the slag layer can be achieved.
the process according to the invention is advantageously carried out in such a way that the granular and the lumpy portion of the desulfurizing agent is introduced above or laterally into the carbon fluidized bed.
the desulphurising agent can be easily introduced together with coal, aggregates or recycling materials.
the desulfurizing agents are at least partially introduced in agglomerated form.
the invention is explained in more detail below using an exemplary embodiment.
About 1000 kg of coal were used in a smelting gasifier per ton of pig iron.
the coal had a sulfur content of 1.0%.
the sulfur was composed of 60% organically bound sulfur and 40% inorganic sulfur (pyrite, sulfide, sulfate-S). Most of the inorganic sulfur was released when the coal was degassed and went into the reducing gas.
the remaining sulfur approx. 6 - 7 kg / t pig iron, was converted into the gaseous state in the fluidized bed during combustion in front of the nozzles or gasification of the coked coal (S-Dampf, S0 2 , COS).
the reaction product CaS dissolved in the slag.
the sulfur content of the slag was between 2 and 3% and the sulfur in pig iron was 0.1%.

Landscapes

Engineering & Computer Science (AREA)
Chemical & Material Sciences (AREA)
Manufacturing & Machinery (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)

EP84890076A 1983-05-04 1984-04-26 Procédé pour éliminer le soufre pendant la fusion de fonte brute Expired EP0128131B1 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
AT0164683A AT387036B (de)	1983-05-04	1983-05-04	Verfahren zum entfernen von schwefel bei der erschmelzung von roheisen
AT1646/83		1983-05-04

Publications (2)

Publication Number	Publication Date
EP0128131A1 true EP0128131A1 (fr)	1984-12-12
EP0128131B1 EP0128131B1 (fr)	1987-04-01

Family

ID=3517920

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP84890076A Expired EP0128131B1 (fr)	1983-05-04	1984-04-26	Procédé pour éliminer le soufre pendant la fusion de fonte brute

Country Status (5)

Country	Link
US (1)	US4566902A (fr)
EP (1)	EP0128131B1 (fr)
JP (1)	JPS59208007A (fr)
AT (1)	AT387036B (fr)
DE (1)	DE3462925D1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
AT388176B (de) *	1987-07-30	1989-05-10	Voest Alpine Ag	Verfahren und anlage zur gewinnung von fluessigem roheisen oder stahlvorprodukten aus stueckigen, eisenoxidhaeltigen einsatzstoffen
CN115044402B (zh) *	2022-06-13	2023-04-25	太原理工大学	一种煤的原位高温溶浸脱硫方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE1160457B (de) *	1955-06-18	1964-01-02	Knapsack Ag	Verfahren zur Kokseinsparung und Leistungssteigerung bei der Herstellung von Roheisen im Hochofen
DE2607554A1 (de) *	1975-03-03	1976-09-09	Stora Kopparbergs Bergslags Ab	Verfahren zur reduktion von feinkoernigen eisenoxidhaltigen materialien in einer wirbelschicht
US4260412A (en) *	1980-01-16	1981-04-07	Midrex Corporation	Method of producing direct reduced iron with fluid bed coal gasification
EP0010627B1 (fr) *	1978-10-04	1981-12-02	Korf-Stahl AG	Procédé et dispositif pour la production de fonte brute liquide et de gaz réducteur dans un récipient de fusion et de gazéification
DE3216019A1 (de) *	1981-06-10	1983-01-27	Sumitomo Metal Industries, Ltd., Osaka	Kohlevergasung und roheisenherstellung und vorrichtung dafuer

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE1153395B (de) *	1953-05-29	1963-08-29	Werner Wenzel Dr Ing	Verfahren zur Eisengewinnung aus in der Schwebe befindlichen, staub-foermigen bzw. feinkoernigen Eisenerzen mittels Brennstoffen in feinem Verteilungs-grad
DE2133860A1 (en) *	1970-07-07	1972-01-13	Barker, Arnold Verdun, Palm Beach, New South Wales (Australien)	Direct reduction of iron ore - using cyclone furnace and electric arc or induction furnace
US3948640A (en) *	1973-04-30	1976-04-06	Boliden Aktiebolag	Method of carrying out heat-requiring chemical and/or physical processes
DE2401909C3 (de) *	1974-01-16	1985-06-27	Fried. Krupp Gmbh, 4300 Essen	Verfahren zur Herstellung von Stahl

1983
- 1983-05-04 AT AT0164683A patent/AT387036B/de not_active IP Right Cessation
1984
- 1984-04-26 EP EP84890076A patent/EP0128131B1/fr not_active Expired
- 1984-04-26 DE DE8484890076T patent/DE3462925D1/de not_active Expired
- 1984-04-30 US US06/605,282 patent/US4566902A/en not_active Expired - Fee Related
- 1984-05-04 JP JP59090086A patent/JPS59208007A/ja active Granted

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE1160457B (de) *	1955-06-18	1964-01-02	Knapsack Ag	Verfahren zur Kokseinsparung und Leistungssteigerung bei der Herstellung von Roheisen im Hochofen
DE2607554A1 (de) *	1975-03-03	1976-09-09	Stora Kopparbergs Bergslags Ab	Verfahren zur reduktion von feinkoernigen eisenoxidhaltigen materialien in einer wirbelschicht
EP0010627B1 (fr) *	1978-10-04	1981-12-02	Korf-Stahl AG	Procédé et dispositif pour la production de fonte brute liquide et de gaz réducteur dans un récipient de fusion et de gazéification
US4260412A (en) *	1980-01-16	1981-04-07	Midrex Corporation	Method of producing direct reduced iron with fluid bed coal gasification
DE3216019A1 (de) *	1981-06-10	1983-01-27	Sumitomo Metal Industries, Ltd., Osaka	Kohlevergasung und roheisenherstellung und vorrichtung dafuer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
STAHL UND EISEN, Band 102, Nr. 19, 20. September 1982, Düsseldorf; "Das Kohlereduktionsverfahren (KR-Verfahren) zur Roheisenerzeugung aus Erz und Rohkohle",Seiten 35, 36 *

Also Published As

Publication number	Publication date
AT387036B (de)	1988-11-25
JPS59208007A (ja)	1984-11-26
JPH046767B2 (fr)	1992-02-06
ATA164683A (de)	1988-04-15
DE3462925D1 (en)	1987-05-07
US4566902A (en)	1986-01-28
EP0128131B1 (fr)	1987-04-01

Legal Events

Date	Code	Title	Description
1984-10-15	PUAI	Public reference made under article 153(3) epc to a published international application that has entered the european phase	Free format text: ORIGINAL CODE: 0009012
1984-12-12	AK	Designated contracting states	Designated state(s): BE DE FR GB IT LU NL SE
1985-03-06	17P	Request for examination filed	Effective date: 19841218
1986-12-03	ITF	It: translation for a ep patent filed
1987-02-14	GRAA	(expected) grant	Free format text: ORIGINAL CODE: 0009210
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1988-02-03	PLBE	No opposition filed within time limit	Free format text: ORIGINAL CODE: 0009261
1988-02-03	STAA	Information on the status of an ep patent application or granted ep patent	Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT
1988-03-23	26N	No opposition filed
1990-03-15	PGFP	Annual fee paid to national office [announced via postgrant information from national office to epo]	Ref country code: FR Payment date: 19900315 Year of fee payment: 7
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DE69809958T2 (de)	2003-12-11	Verfahren zur herstellung von eisen und stahl
EP0164592B2 (fr)	1991-08-14	Agent de désulfuration à grain fin pour des bains de fonte brute et procédé de désulfuration
US4139369A (en)	1979-02-13	Desulphurization of an iron melt
DE4242328C2 (de)	1995-06-08	Mittel zur Entschwefelung, Entphosphorung, Entsilicierung und Entstickung von Roheisen- und Gußeisenschmelzen
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AT405054B (de)	1999-05-25	Verfahren und anlage zum herstellen einer eisenschmelze unter einsatz von eisenhältigen hüttenwerksreststoffen
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WO2012095471A2 (fr)	2012-07-19	Agent de traitement pour métaux en fusion, procédé de production et utilisation de cet agent
DE3118288A1 (de)	1982-04-08	Pulverfoermige entschwefelungsmasse
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US2727815A (en)	1955-12-20	Method for the smelting of iron ores
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DE2037758B2 (de)	1978-11-30	Verfahren zur Herstellung von CaIciumkarbid zur Entschwefelung von Metallschmelzen
DE68913509T2 (de)	1994-09-29	Verfahren zur Herstellung von flüssigem Roheisen.
DE3629589C2 (fr)	1992-04-02
DE3120138A1 (de)	1982-02-25	Pulverfoermiges entschwefelungsmittel
US4323392A (en)	1982-04-06	Agent for desulfurizing crude iron and steel melts, and process for making it
DE4226833A1 (de)	1994-02-17	Entschwefelungsmittel für Roheisen und Gußeisen
DE10217956B4 (de)	2008-04-17	Verfahren zur Phosphor-Rückgewinnung
DE2709062A1 (de)	1978-09-07	Mittel und verfahren zur entschwefelung von eisenschmelzen
US3705795A (en)	1972-12-12	Process of directly reducing materials containing iron oxide in a rotary kiln
US1691274A (en)	1928-11-13	Method of producing dense iron and iron alloys directly out of oxide ores