EP0128131A1 - Sulphur removing method during pig iron melting - Google Patents
Sulphur removing method during pig iron melting Download PDFInfo
- Publication number
- EP0128131A1 EP0128131A1 EP84890076A EP84890076A EP0128131A1 EP 0128131 A1 EP0128131 A1 EP 0128131A1 EP 84890076 A EP84890076 A EP 84890076A EP 84890076 A EP84890076 A EP 84890076A EP 0128131 A1 EP0128131 A1 EP 0128131A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluidized bed
- coal
- lumpy
- desulfurizing
- slag
- 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
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)
Abstract
Zur Entfernung von Schwefel beim Erschmelzen von Roheisen in einer Kohlewirbelschicht wird vorgeschlagen, stückiges und/oder körniges Entschwefelungsmittel zu mindest in die Kohlewirbelschicht einzubringen. Zusätzlich kann das Entschwefelungsmittel in die Schlacke eingebracht werden, wobei vorzugsweise für die Kohlewirbelschicht Entschwefelungsmittel im Korngrößenbereich von 0,5 - 5 mm und für die Schlackenschicht im Korngrößenbereich von 5 bis 50 mm oberhalb oder seitlich der Kohlewirbelschicht aufgegeben werden. Der Anteil der stückigen Entschwefelungsmittel soll vorzugsweise kleiner als 50 Gew.% der gesamten Menge gewählt werden.In order to remove sulfur when melting pig iron in a fluidized bed of coal, it is proposed to introduce at least lumpy and / or granular desulfurizing agent into the fluidized bed of coal. In addition, the desulfurizing agent can be introduced into the slag, desulphurizing agents in the particle size range of 0.5-5 mm preferably being applied for the coal fluidized bed and above or to the side of the carbon fluidized bed for the slag layer in the particle size range of 5 to 50 mm. The proportion of the lumpy desulfurizing agent should preferably be less than 50% by weight of the total amount.
Description
Die Erfindung bezieht sich auf ein Verfahren zum Entfernen von Schwefel bei der Erschmelzung von Roheisen in einer Kohlewirbelschicht.The invention relates to a method for removing sulfur in the melting of pig iron in a coal fluidized bed.
Für das Schmelzen von zumindest teilweise reduziertem Eisenerz, insbesondere Eisenschwamm, wurden Verfahren vorgeschlagen, welche unter Verwendung eines Einschmelzvergasers arbeiten, in welchem durch eingebrachte Kohle und eingeblasenes sauerstoffhaltiges Gas die zum Schmelzen des reduzierten Materials erforderliche Wärme und ein Reduktionsgas erzeugt werden. Ein derartiges Einschmelzverfahren ist beispielsweise der DE-OS 28 43 303 zu entnehmen. Derartige Reduktionsverfahren wurden vor allen Dingen im Hinblick auf die Verwendung von schlecht oder nicht verkokbaren Kohlenstoffträgern entwickelt, welche sich durch einen relativ hohen Schwefelgehalt auszeichnen. Bei derartigenoVerfahrensweisen wird somit ein hoher Schwefelanteil über die Kohle in das Bad eingebracht und es ist der Schwefelgehalt im Metall üblicherweise wesentlich größer als der Schwefelgehalt im vergleichbaren Hochofenroheisen. Die Reaktion in derartigen Einschmelzvergasern läuft relativ rasch ab, und auf Grund des raschen Materialdurchganges durch das Wirbelbett wird üblicherweise nur ein geringer Siliziumgehalt von unter 0,2 % und ein FeO-Gehalt in der Schlacke erzielt, welcher höher liegt als der FeO-Gehalt in einer Hochofenschlacke. Beide dieser Tatsachen beeinträchtigen die Entschwefelungsreaktion mit Kalk.For the melting of at least partially reduced iron ore, in particular sponge iron, methods have been proposed which operate using a melter gasifier, in which the heat required for melting the reduced material and a reducing gas are generated by introduced coal and injected oxygen-containing gas. Such a melting process can be found, for example, in DE-OS 28 43 303. Such reduction processes were primarily developed with a view to using poorly or non-coking carbon carriers, which are distinguished by a relatively high sulfur content. In such procedures, a high proportion of sulfur is thus introduced into the bath via the coal, and the sulfur content in the metal is usually significantly higher than the sulfur content in comparable blast furnace pig iron. The reaction in such melter gasifiers takes place relatively quickly, and due to the rapid passage of material through the fluidized bed, usually only a low silicon content of less than 0.2% and an FeO content in the slag which is higher than the FeO content in a blast furnace slag. Both of these facts affect the desulfurization reaction with lime.
Eine ausreichende Entschwefelung von mit derartigen Verfahren erschmolzenem Roheisen konnte daher bisher nur in der Pfanne und damit unter zusätzlichem Energieverbrauch sinnvoll erzielt werden.Adequate desulphurization of pig iron melted using such processes has thus far only been sensible in the pan and thus with additional energy consumption.
Die Erfindung zielt nun darauf ab, eine derartige gesonderte Entschwefelung der Schmelze zu vermeiden und den Großteil oder die gesamte Entschwefelungsarbeit bereits in dem Schmelzreaktor vorzunehmen. Zur Lösung dieser Aufgabe besteht die Erfindung im wesentlichen darin, daß stückiges und/oder körniges Entschwefelungsmittel in die Kohlewirbelschicht und gegebenenfalls zusätzlich in die Schlackenschicht eingebracht wird. Eine Verwendung von staubförmigen Feinkalk in Form von Kalkhydrat oder gebranntem Kalk hat sich als nachteilig herausgestellt, da staubförmiger Feinkalk zum Großteil mit dem eingeblasenem Gas wieder ausge-tragen wird, und nur ein mengenmäßig geringer Anteil für die Entschwefelung im Schmelzraum zur Verfügung steht. Die ausschließliche Verwendung von stückigem Brandkalk führt auf Grund der Bildung einer Dicalciumsilikatschicht an der Kornoberfläche zu einer ungenügenden Auflösung in der meist sauren Schlacke aus der Kohlenasche. Die Verwendung von körnigem Entschwefelungsmittel in der Kohlewirbelschicht. erlaubt es, einen Großteil der Entschwefelungsarbeit bereits'während der Schmelzreduktionsvorgänge in der fluidisierten Phase durchzuführen und die zusätzliche Zugabe von stückigem Entschwefelungsmittel, welches in der Kohlewirbelschicht nicht gänzlich reagiert, führt zu einer weiteren Entschwefelung durch Austauschvorgänge in der Grenzzone von Schlacke und Wirbelbett.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. To achieve this object, 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 use of granular desulfurizing agents in the coal bed. allows a large part of the desulphurization work to be carried out during the smelting reduction processes in the fluidized phase and the additional addition of lumpy desulphurising agents, which do not react completely in the coal fluidized bed, leads to further desulphurization through exchange processes in the boundary zone between slag and fluidized bed.
Die Entschwefelungsreaktion mit CaO ist endotherm und läuft in Richtung höherer Temperaturen bevorzugt ab.
Auf Grund dieses Faktums und wegen des hohen Schwefeleinbringens durch die Kohle wird im Kohlewirbelbett erschmolzenes Roheisen im Schwefelgehalt immer deutlich höher liegen als Hochofenroheisen. Eine Entschwefelung außerhalb des Schmelzgefäßes mit großen spezifischen Mengen der bekannten Entschwefelungsmittel Calciumkarbid, Soda, Magnesium usw. ist daher notwendig. Erfindungsgemäß werden nun die zur Nachentschwefelung vorgesehenen Einsatzstoffe in körniger und/oder stückiger Form schon in den Einschmelzgenerator zudosiert und entsprechend ihrer Korngröße zusammen mit der Kohle gewirbelt. Sie binden dabei in festem, flüssigem oder sublimierten Aggregatzustand den Kohleschwefel ab oder fallen im Falle einer gröberen Körnung sofort durch die Wirbelschicht hindurch und lösen sich in engem Kontakt mit dem aufschmelzenden Eisenschwamm langsam in der Schlackenschicht auf. Durch Variation des stückigen bzw. des körnigen Anteils des Entschwefelungsmittels kann das Schwergewicht der Entschwefelungsreaktion in die Wirbelschicht bzw. in die Schlakkenschicht verlagert werden.Because of this fact and because of the high sulfur input from the coal is in the coal fluidized bed molten pig iron always has a significantly higher sulfur content than blast furnace pig iron. Desulfurization outside the melting vessel with large specific amounts of the known desulfurizing agents calcium carbide, soda, magnesium, etc. is therefore necessary. According to the invention, 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.
Im Rahmen des erfindungsgemäßen Verfahrens können als Entschwefelungsmittel Mangan Calcium, Magnesium, Alkalien oder seltene Erden in Form von Oxiden, Carbiden, Karbonaten, Legierungen, Mischmetallen oder in metallischer Form eingesetzt werden. Die Verwendung von Calciumkarbonat allein hat jedoch den Nachteil, daß bei einer direkten Chargierung in den Vergaser nicht unbeträchtliche Energiemengen für die Austreibung und Umsetzung von C02 erforderlich sind. In besonders bevorzugter Weise wird daher erfindungsgemäß Calciumcarbid als Entschwefelungsmittel eingesetzt. Die Entschwefelungsreaktion mit CaC2 läuft unter Energieabgabe und bevorzugt in Richtung niedriger Temperaturen ab.
Calciumcarbid bewirkt auch als Desoxidationsmittei eine Verringerung des FeO-Gehaltes in der Schlacke. Die Reaktionsprodukte CaO und CaS werden von der Schlacke aufgenommen.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.
Die Zugabe von stückigen und/oder körnigen Entschwefelungsnitteln in die Kohlewirbelschicht bringt im Vergleich mit dem Entschwefeln außerhalb des Schmelzgefäßes unter anderem eine optimale Verteilung und lange Aufenthaltsdauer der Entschwefelungsmittel im Wirbelbett bzw. an der Schlackenoberfläche und dadurch ideale kinetische Voraussetzungen mit sich.The addition of lumpy and / or granular desulfurization agents to the carbon fluidized bed, in comparison with desulfurization outside the melting vessel, results in an optimal distribution and long residence time of the desulfurization agents in the fluidized bed or on the slag surface and therefore ideal kinetic conditions.
Leiters ergibt sich eine Steuerungsmöglichkeit durch kombinierte Beaufschlagung der Entschwefelungsräume (Wirbelbett für Kohleentschwefelung und Schlackenschicht für Eisenentschwefelung). Hier spielen Körnung und Qualität des Entschwefelungsmittels eine wichtige Rolle. Eine derartige Steuerungsmöglichkeit wird in vorteilhafter Weise dadurch erzielt, daß der Anteil des Entschwefelungsmittels für die Kohlewirbelschicht im Korngrößenbereich von 0,5 - 5 mm und der Anteil des Entschwefelungsmittels für die Schlacke im Korngrößenbereich von 5 - 50 mm eingebracht wird, wobei diese beiden Anteile in weiten Grenzen variiert werden können und auf diese Weise eine Einstellung des Schwergewichtes der Entschwefelungsreaktion auf das Wirbelbett oder die Schlakkenschicht erzielt werden kann.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.
Weitere Vorteile der Zugabe von stückigem und/oder körnigem Entschwefelungsmittel direkt in die Kohlewirbelschicht bzw. unmittelbar auf das Bad im Einschmelzreaktor ergeben sich im Gegensatz zur Entschwefelung außerhalb des Reaktors aus der besseren energetischen und mengenmäßigen Nutzung der Entschwefelungsmittel. Da der Entschwefelungsprozeß gleichzeitig mit dem Schmelzprozeß abläuft, kann man zusätzliche Behandlungszeiten und davon abhängige Energie- verluste zumindest wesentlich einschränken. Die über die Entschwefelungsmittel eingebrachte chemische Energie (z.B. der Kohlenstoff des CaC2) wird im geschlossenen Schmelzgefäß besser ausgenützt als in der Pfanne.In contrast to desulfurization outside the reactor, further advantages of adding lumpy and / or granular desulfurizing agents directly into the carbon fluidized bed or directly onto the bath in the melting reactor result from the better use of the desulfurizing agents in terms of energy and quantity. Since the desulfurization process takes place at the same time as the melting process, additional treatment times and dependent energy losses can at least be significantly reduced. The chemical energy introduced via the desulfurization agents (eg the carbon of the CaC 2 ) is better used in the closed melting vessel than in the pan.
In vorteilhafter Weise wird im Rahmen des erfindungsgemäßen Verfahrens so vorgegangen, daß der körnige und der stückige Anteil des Entschwefelungsmittels oberhalb der Kohlewirbelschicht oder seitlich in diese aufgegeben wird. Hiebei kann das Entschwefelungsmittel in einfacher Weise zusammen mit Kohle, Zuschlags- oder Kreislaufstoffen eingebracht werden.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.
Zur Einstellung der günstigsten Korngrößen ist es vorteilhaft, wenn die Entschwefelungsmittel zumindest teilweise in agglomerierter Form eingebracht werden.To set the most favorable grain sizes, it is advantageous if the desulfurizing agents are at least partially introduced in agglomerated form.
Die Erfindung wird nachfolgend an Hand eines Ausführungsbeispieles näher erläutert. Pro Tonne Roheisen wurden in einem Einschmelzvergaser etwa 1000 kg Kohle eingesetzt. Die Kohle hatte einen Schwefelgehalt von 1,0%. Der Schwefel setzte sich aus 60% organisch gebundenem Schwefel und 40% anorganischem Schwefel (Pyrit, Sulfide, Sulfat-S) zusammen. Der größte Teil an anorganischem Schwefel wurde bei der Entgasung der Kohle frei und ging ins Reduktionsgas. Der Restschwefel, ca. 6 - 7 kg/t Roheisen, wurde im Wirbelbett bei der Verbrennung vor den Düsen bzw. Vergasung der verkokten Kohle in den gasförmigen Zustand übergeführt (S-Dampf, S02, COS). Bei der Wirbelung kam der gasförmige Schwefel mit dem feinkörnigen CaC2 in Kontakt und wurde zu CaS abgebunden. Etwa 4 kg S wurden auf diese Weise in CaS übergeführt. Die restlichen 3 kg wurden entweder vom Zuschlagskalk oder vom heißen Eisenschwamm, der durch das Wirbelbett hindurchfiel, absorbiert. Der FeS-hältige Eisenschwamm wurde anschließend beim Kontakt mit dem auf der Schlackenoberfläche schwimmenden stückigen Calciumcarbid entschwefelt.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). During the swirling, the gaseous sulfur came into contact with the fine-grained CaC 2 and was bound to CaS. About 4 kg of S were converted into CaS in this way. The remaining 3 kg were absorbed either by the aggregate lime or by the hot sponge iron that fell through the fluidized bed. The FeS-containing sponge iron was then desulfurized on contact with the lumpy calcium carbide floating on the slag surface.
Bei einem Ausnutzungsgrad von 80% des eingesetzten Calciumcarbids ergab sich nachfolgende Gleichung:
- 12 kg CaC2 + 6 kg S = 13,5 kg CaS + 4,5 kg C ein Bedarf von 15 kg CaC2, wobei 2/3 in körniger und 1/3 in stückiger Form chargiert wurde.
- 12 kg CaC 2 + 6 kg S = 13.5 kg CaS + 4.5 kg C a requirement of 15 kg CaC 2 , with 2/3 being charged in granular and 1/3 in lumpy form.
Das Reaktionsprodukt CaS löste sich in der Schlacke. Je nach spezifischer Schlackenmenge lag der Schwefelgehalt der Schlacke zwischen 2 und 3% und der Schwefel im Roheisen bei 0,1%.The reaction product CaS dissolved in the slag. Depending on the specific amount of slag, the sulfur content of the slag was between 2 and 3% and the sulfur in pig iron was 0.1%.
Claims (9)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0164683A AT387036B (en) | 1983-05-04 | 1983-05-04 | METHOD FOR THE REMOVAL OF SULFUR FROM THE MELTING OF RAW IRON |
| AT1646/83 | 1983-05-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0128131A1 true EP0128131A1 (en) | 1984-12-12 |
| EP0128131B1 EP0128131B1 (en) | 1987-04-01 |
Family
ID=3517920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84890076A Expired EP0128131B1 (en) | 1983-05-04 | 1984-04-26 | Sulphur removing method during pig iron melting |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4566902A (en) |
| EP (1) | EP0128131B1 (en) |
| JP (1) | JPS59208007A (en) |
| AT (1) | AT387036B (en) |
| DE (1) | DE3462925D1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT388176B (en) * | 1987-07-30 | 1989-05-10 | Voest Alpine Ag | METHOD AND PLANT FOR THE PRODUCTION OF LIQUID RAW IRON OR STEEL PRE-PRODUCTS FROM LIQUID, IRON OXIDE-CONTAINING MATERIALS |
| CN115044402B (en) * | 2022-06-13 | 2023-04-25 | 太原理工大学 | A method for in-situ high-temperature leaching desulfurization of coal |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1160457B (en) * | 1955-06-18 | 1964-01-02 | Knapsack Ag | Process for saving coke and increasing performance in the production of pig iron in the blast furnace |
| DE2607554A1 (en) * | 1975-03-03 | 1976-09-09 | Stora Kopparbergs Bergslags Ab | PROCESS FOR THE REDUCTION OF FINE-GRAY FINE-GRAIN FERROUS MATERIALS IN A FLUIDED LAYER |
| US4260412A (en) * | 1980-01-16 | 1981-04-07 | Midrex Corporation | Method of producing direct reduced iron with fluid bed coal gasification |
| EP0010627B1 (en) * | 1978-10-04 | 1981-12-02 | Korf-Stahl AG | Method and apparatus for making liquid pig iron and reducing gas in a smelting down and gasification vessel |
| DE3216019A1 (en) * | 1981-06-10 | 1983-01-27 | Sumitomo Metal Industries, Ltd., Osaka | CARBON GASIFICATION AND PIG IRON PRODUCTION AND DEVICE THEREFOR |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1153395B (en) * | 1953-05-29 | 1963-08-29 | Werner Wenzel Dr Ing | Process for iron extraction from suspended, dusty or fine-grained iron ores using fuels with a fine degree of distribution |
| 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 |
| US3948645A (en) * | 1973-04-30 | 1976-04-06 | Boliden Aktiebolag | Method of carrying out heat-requiring chemical and/or physical processes in a fluidized bed |
| DE2401909C3 (en) * | 1974-01-16 | 1985-06-27 | Fried. Krupp Gmbh, 4300 Essen | Process for the production of steel |
-
1983
- 1983-05-04 AT AT0164683A patent/AT387036B/en not_active IP Right Cessation
-
1984
- 1984-04-26 EP EP84890076A patent/EP0128131B1/en not_active Expired
- 1984-04-26 DE DE8484890076T patent/DE3462925D1/en 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/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1160457B (en) * | 1955-06-18 | 1964-01-02 | Knapsack Ag | Process for saving coke and increasing performance in the production of pig iron in the blast furnace |
| DE2607554A1 (en) * | 1975-03-03 | 1976-09-09 | Stora Kopparbergs Bergslags Ab | PROCESS FOR THE REDUCTION OF FINE-GRAY FINE-GRAIN FERROUS MATERIALS IN A FLUIDED LAYER |
| EP0010627B1 (en) * | 1978-10-04 | 1981-12-02 | Korf-Stahl AG | Method and apparatus for making liquid pig iron and reducing gas in a smelting down and gasification vessel |
| US4260412A (en) * | 1980-01-16 | 1981-04-07 | Midrex Corporation | Method of producing direct reduced iron with fluid bed coal gasification |
| DE3216019A1 (en) * | 1981-06-10 | 1983-01-27 | Sumitomo Metal Industries, Ltd., Osaka | CARBON GASIFICATION AND PIG IRON PRODUCTION AND DEVICE THEREFOR |
Non-Patent Citations (1)
| 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 |
|---|---|
| US4566902A (en) | 1986-01-28 |
| JPS59208007A (en) | 1984-11-26 |
| EP0128131B1 (en) | 1987-04-01 |
| DE3462925D1 (en) | 1987-05-07 |
| AT387036B (en) | 1988-11-25 |
| ATA164683A (en) | 1988-04-15 |
| JPH046767B2 (en) | 1992-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69809958T2 (en) | METHOD FOR PRODUCING IRON AND STEEL | |
| EP0164592B2 (en) | Fine-grained desulfurization agent forron melts, and process for the desulfurization of molten pig iron | |
| US4139369A (en) | Desulphurization of an iron melt | |
| DE4242328C2 (en) | Means for desulfurization, dephosphorization, desiliconization and denitrification of pig iron and cast iron melts | |
| EP1198599B1 (en) | Method for conditioning slag with the addition of metallurgical residual materials and an installation for the same | |
| DE69703020T2 (en) | Melting of nickel laterite and sulfur-containing nickel concentrate to produce nickel-alloyed iron and stainless steel | |
| EP0061012B1 (en) | Process for producing desulfurizing agents for pig iron and steel melts | |
| AT405054B (en) | METHOD AND PLANT FOR PRODUCING AN IRON MEL WITH THE USE OF IRON-CONTAINING RESIDUAL MATERIALS | |
| WO2012095471A2 (en) | Agent for treating molten metals, method for the production and use thereof | |
| DE3347685C1 (en) | Process for the production of ferromanganese | |
| DE3118288A1 (en) | POWDERED DESULFURATION MASS | |
| EP0128131B1 (en) | Sulphur removing method during pig iron melting | |
| US2727815A (en) | Method for the smelting of iron ores | |
| EP0676478A1 (en) | Process for producing an iron melt | |
| RU2103377C1 (en) | Burden for preparation of material for metallurgy and process of its preparation | |
| EP2427581B1 (en) | Process for slag foaming a non-stainless steel melt in an electric arc furnace | |
| DE2037758B2 (en) | Process for the production of calcium carbide for the desulfurization of metal melts | |
| DE68913509T2 (en) | Process for the production of molten pig iron. | |
| DE3629589C2 (en) | ||
| DE3120138A1 (en) | POWDERED DESULFURING AGENT | |
| US4323392A (en) | Agent for desulfurizing crude iron and steel melts, and process for making it | |
| DE4226833A1 (en) | Desulphurising agent for pig iron and cast iron | |
| US3705795A (en) | Process of directly reducing materials containing iron oxide in a rotary kiln | |
| DE10217956A1 (en) | Recovery of phosphorus from waste materials comprises fusing waste materials with lime to form liquid slag and grinding solidified slag to produce product useful as slow release fertilizer | |
| US1691274A (en) | Method of producing dense iron and iron alloys directly out of oxide ores |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 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 |
|
| AK | Designated contracting states |
Designated state(s): BE DE FR GB IT LU NL SE |
|
| 17P | Request for examination filed |
Effective date: 19841218 |
|
| ITF | It: translation for a ep patent filed | ||
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE FR GB IT LU NL SE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19870430 |
|
| REF | Corresponds to: |
Ref document number: 3462925 Country of ref document: DE Date of ref document: 19870507 |
|
| ET | Fr: translation filed | ||
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| 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 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19900319 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19900323 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: LU Payment date: 19900329 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19900331 Year of fee payment: 7 |
|
| ITTA | It: last paid annual fee | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19900430 Year of fee payment: 7 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19910426 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19910427 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Effective date: 19910430 |
|
| BERE | Be: lapsed |
Owner name: VOEST-ALPINE A.G. Effective date: 19910430 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19911101 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19911230 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
| EUG | Se: european patent has lapsed |
Ref document number: 84890076.7 Effective date: 19911108 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20000320 Year of fee payment: 17 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020201 |