EP3572534A1 - Desulfurization treatment method for molten steel, and desulfurization agent - Google Patents
Desulfurization treatment method for molten steel, and desulfurization agent Download PDFInfo
- Publication number
- EP3572534A1 EP3572534A1 EP18741544.3A EP18741544A EP3572534A1 EP 3572534 A1 EP3572534 A1 EP 3572534A1 EP 18741544 A EP18741544 A EP 18741544A EP 3572534 A1 EP3572534 A1 EP 3572534A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- molten steel
- desulfurization
- quicklime
- ladle
- processing
- 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
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 153
- 230000023556 desulfurization Effects 0.000 title claims abstract description 153
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 132
- 239000010959 steel Substances 0.000 title claims abstract description 132
- 238000000034 method Methods 0.000 title description 31
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 143
- 238000012545 processing Methods 0.000 claims abstract description 103
- 239000000292 calcium oxide Substances 0.000 claims abstract description 69
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 69
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 239000011148 porous material Substances 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 30
- 239000011593 sulfur Substances 0.000 claims abstract description 30
- 238000003672 processing method Methods 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 29
- 238000010079 rubber tapping Methods 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000004907 flux Effects 0.000 abstract description 24
- 239000002893 slag Substances 0.000 description 70
- 239000000463 material Substances 0.000 description 42
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 30
- 238000012360 testing method Methods 0.000 description 19
- 229910000805 Pig iron Inorganic materials 0.000 description 18
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 16
- 229910001634 calcium fluoride Inorganic materials 0.000 description 15
- 239000000395 magnesium oxide Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 238000007670 refining Methods 0.000 description 15
- 238000007664 blowing Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000010459 dolomite Substances 0.000 description 10
- 229910000514 dolomite Inorganic materials 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 230000001965 increasing effect Effects 0.000 description 9
- 238000005261 decarburization Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000011449 brick Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910000882 Ca alloy Inorganic materials 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010436 fluorite Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- 229910014458 Ca-Si Inorganic materials 0.000 description 1
- 229910002974 CaO–SiO2 Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910018619 Si-Fe Inorganic materials 0.000 description 1
- 229910008289 Si—Fe Inorganic materials 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VMXUWOKSQNHOCA-UKTHLTGXSA-N ranitidine Chemical compound [O-][N+](=O)\C=C(/NC)NCCSCC1=CC=C(CN(C)C)O1 VMXUWOKSQNHOCA-UKTHLTGXSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0075—Treating in a ladle furnace, e.g. up-/reheating of molten steel within the ladle
-
- 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
-
- 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
-
- 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
- C21C7/072—Treatment with gases
-
- 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
- C21C7/076—Use of slags or fluxes as treating agents
Definitions
- the present invention relates to a desulfurization processing method of molten steel and a desulfurization agent.
- the desulfurization processing at the molten steel stage is typically performed by a ladle refining method such as an ASEA-SKF method, a VAD method, or an LF method.
- the ladle reining method includes an arc heating means to heat molten steel and a stirring means to stir molten steel, and further includes a blowing means to blow powder such as flux or alloy powder to molten steel.
- a desulfurization agent is added into a ladle holding molten steel manufactured by being melted by decarburization refining in a converter, the molten steel and the desulfurization agent are stirred and mixed with each other or subjected to arc heating, thereby causing the desulfurization agent to form slag, and a slag-metal reaction occurs between the slag formed by slag formation of the desulfurization agent and the molten steel to transfer sulfur in the molten steel to the slag.
- the used desulfurization agent contains CaO (quicklime) as a major component and Al 2 O 3 (alumina), CaF 2 (fluorite), and the like, which are added for the purpose of lowering a melting point of the desulfurization agent.
- CaO quicklime
- Al 2 O 3 alumina
- CaF 2 fluorite
- the desulfurization agent is typically added to molten steel in the ladle by being placed on the molten steel. It takes a long time that the desulfurization agent forms slag in any case where the desulfurization agent forms slag by arc heating or by being stirred and mixed with the molten steel after the desulfurization agent is added.
- Patent Literature 1 discloses a method of desulfurizing molten steel in which flux, a mixture of quicklime, alumina, and fluorite, is added and bubbling processing is performed such that a slag composition after the desulfurization processing satisfies that CaO/Al 2 O 3 ⁇ 1.5 mass% and CaF 2 ⁇ 5 mass%.
- Patent Literature 2 discloses a method in which pre-melt flux (preliminarily mixed or uniformly dissolved) of CaO-Al 2 O 3 or pre-melt flux of CaO-Al 2 O 3 -CaF 2 is used for promoting the slag formation of the desulfurization agent.
- Patent Literatures 3, 4, and 5 disclose a method in which stirring gas mixed with flux is blown, as a means to enhance the stirring strength without increasing a stirring gas flow rate.
- Patent Literature 1 has a problem in that, when a desulfurization agent containing CaF 2 is used, refractory forming the ladle is heavily melted and eroded by CaF 2 in the produced slag, thereby significantly shortening a life-span of the ladle.
- the method described in Patent Literature 2 has a problem in that the pre-melt flux is very expensive, thereby increasing processing cost.
- the desulfurization agent containing CaF 2 has the same problem as described above.
- Patent Literatures 3, 4, and 5 has a limit for a flux blowing amount with respect to a blowing gas rate (a solid-gas ratio has a limit ranging from 5 to 30 kg/kg).
- the method thus, has a limit for increasing stirring strength.
- a stirring gas flow rate is increased, a surface of molten steel in the ladle is heavily disturbed (waved).
- a problem arises in that splashes occur and metal sticks to a lid of the ladle, or another problem arises in that electrodes and molten steel are shorted, for example, to cause unstable arc, thereby making it difficult to perform arc heating.
- the invention is made in view of above problems, and aims to provide a desulfurization processing method of molten steel and a desulfurization agent that can efficiently perform desulfurization processing without using CaF 2 and pre-melt flux.
- a desulfurization processing method of molten steel is a method including: adding a desulfurization agent containing quicklime into a ladle holding the molten steel; and stirring the molten steel in the ladle to reduce a sulfur concentration in the molten steel, wherein the desulfurization agent contains quicklime, where a sum of volumes of pores having a pore diameter ranging from 0.5 ⁇ m to 10 ⁇ m (inclusive of 0.5 ⁇ m and 10 ⁇ m) in the quicklime is equal to or larger than 0.1 mL/g.
- the quicklime contains particles, where 90% or more of the particles contained in the quicklime has a particle diameter ranging from 1 mm to 30 mm (inclusive of 1 mm and 30 mm) .
- a desulfurization agent according to the present invention includes quicklime, where a sum of volumes of pores having a pore diameter ranging from 0.5 ⁇ m to 10 ⁇ m (inclusive of 0.5 ⁇ m and 10 ⁇ m) in the quicklime is equal to or larger than 0.1 mL/g, wherein the quicklime contains particles, where 90% or more of the particles contained in the quicklime has a particle diameter ranging from 1 mm to 30 mm (inclusive of 1 mm and 30 mm).
- the stirring is performed so as to satisfy a stirring power density represented by the following formula (1).
- Nm 3 means a volume of gas at an atmospheric pressure of 101325 Pa and a temperature of 273.15 K under standard conditions.
- Al 1 Al conentration standard upper limit mass % in steel grade to be manufactured by being melted sol .
- Al 2 Al concentration mass % in molten steel after tapping from converter
- W Al amount kg / t of Al supplied within 10 minutes after start of ladle desulfurization processing
- argon gas is blown into the ladle such that an oxygen concentration in the ladle is equal to or smaller than 15%.
- the desulfurization processing method of molten steel and the desulfurization agent according to the invention can efficiently perform desulfurization processing without using CaF 2 and pre-melt flux.
- the inventors of the invention have earnestly studied for solving the problems described above by focusing attention on a particle size and a pore diameter of caustic lime and molten steel components. More specifically, the inventors of the invention have performed various experiments and researches for the purpose of causing flux added as a desulfurization agent to rapidly form slag to achieve efficient desulfurization processing without using CaF 2 as a part of the desulfurization agent when low sulfur steel having a sulfur concentration equal to or smaller than 0.0030 mass% is manufactured by being melted by desulfurization processing by a ladle refining method using a desulfurization agent having a CaO containing material as a major constituent material.
- the inventors of the invention have found that the temperature of molten steel when flux is added, a sol. Al concentration, and the particle size and the pore diameter of caustic lime are important in order to promote flux added as a desulfurization agent to form slag.
- the temperature of molten steel is determined by the temperature of molten steel when the molten steel is tapped from a converter. As the temperature of the molten steel when the molten steel is tapped is increased, the refractory of the converter is increasingly melted and eroded, thereby causing processing cost to be increased. An immoderate increase in tapping temperature is, thus, inadvisable.
- the inventors of the invention have found that the desulfurization processing can be performed highly efficiently using a powder desulfurization agent containing quicklime as a major component and the quicklime satisfies that a sum of volumes of pores having a pore diameter ranging from 0.5 to 10 ⁇ m in all of the pores included in the quicklime is equal to or larger than 0.1 mL/g.
- the inventors of the invention thus, have conceived the invention.
- the pore diameter distribution of quicklime was measured by the following method.
- quicklime was dried at a constant temperature of 120 °C for 4 hours.
- Micromerities autopore IV 9520 a pore diameter distribution of dried quicklime having a pore diameter ranging from approximately 0.0036 to 200 ⁇ m was obtained by a mercury intrusion method, and a cumulative pore volume curve was calculated.
- a sum of volumes of pores having a pore diameter ranging from 0.5 to 10 ⁇ m was obtained from the calculated cumulative pore volume curve.
- the pore diameter was calculated using Washburn's equation represented in the following formula (3).
- P is the pressure
- D is the pore diameter
- P ⁇ D ⁇ 4 ⁇ ⁇ ⁇ cos ⁇ ⁇
- Molten pig iron tapped from a blast furnace is received by a hot metal transfer vessel such as a hot metal ladle or a torpedo car, and transferred to a converter in which decarburization refining is performed as the next process.
- a hot metal transfer vessel such as a hot metal ladle or a torpedo car
- hot metal pretreatment such as desulfurization processing and dephosphorization processing are performed on molten pig iron.
- the invention is the technique to manufacture low sulfur steel.
- the desulfurization processing is, thus, performed. Even when the dephosphorization processing is not required in accordance with the compositional standard of the low sulfur steel, the dephosphorization processing is performed to prevent rephosphorization from converter slag in desulfurization processing after tapping from the converter.
- the decarburization refining is performed on the molten pig iron on which the desulfurization processing and the dephosphorization processing are performed, and resulting molten steel is tapped to the ladle.
- a little amount of quicklime (CaO) and a little amount of dolomite (MgCO 3 -CaCO 3 ), or calcined dolomite (MgO-CaO) is used as flux, and the flux forms slag in the converter (hereinafter described as the "converter slag"), because the desulfurization processing and the dephosphorization processing are already performed on the molten pig iron.
- the converter slag has a role to promote dephosphorization reaction of the molten pig iron.
- the dephosphorization processing is, however, already performed on the molten pig iron.
- the main role of converter slag is, thus, prevention of occurrence of iron splashes in blowing refining and melting and erosion of the lining refractory of the converter.
- the converter slag is mixed into the molten steel and flows into the ladle.
- Slag flow-out prevention measures which are typically taken, are performed to prevent the flow out of the converter slag. It is, however, difficult to perfectly prevent the converter slag from being flowed out even when the slag flow-out prevention measures are taken.
- Some amount of converter slag is mixed into the molten steel in the ladle and flows out from the converter.
- the converter slag that is mixed into the molten steel and flows into the ladle may be removed from the ladle.
- the converter slag may, however, not be removed because SiO 2 component in the converter slag contributes to the slag formation of a CaO containing material added later as the desulfurization agent.
- CaO-MgO-Al 2 O 3 -SiO 2 desulfurization slag having a certain composition in the ladle
- a CaO containing material, a MgO containing material, an Al 2 O 3 containing material, and a SiO 2 containing material are added into the ladle as flux.
- MgO has a lower desulfurization ability than that of CaO, the MgO containing material may not be added.
- Metallic Al is added into the ladle for deoxidation of the molten steel and reduction of the slag (reduction of Fe oxides and Mn oxides in the slag).
- those materials may be added into a facility in later process that performs desulfurization processing by any of an ASEA-SKF method, a VAD method, and an LF method. From a point of view of promoting the slag formation of CaO, those materials are preferably added into the ladle at tapping from the converter to the ladle or just after the tapping. It is preferable for quicklime added just after the tapping that a sum of volumes of pores having a pore diameter ranging from 0.5 to 10 ⁇ m in all of the pores included in the quicklime is equal to or larger than 0.1 mL/g, and the quicklime contains particles 90% or more of which have a particle diameter ranging from 1 to 30 mm.
- Respective additive amounts of the CaO containing material, the MgO containing material, metallic Al, the Al 2 O 3 containing material, and the SiO 2 containing material are determined, by considering a mass and a component composition of converter slag flowed into the ladle, such that the composition of the slag produced in the ladle after the slag formation of the added flux, i.e., the slag formed from the flux and the converter slag, satisfies that the SiO 2 content is in a range from 5 to 15 mass% and a value of [(mass% CaO) + (mass% MgO)]/(mass% Al 2 O 3 ) is in a range from 1.5 to 3.0, and, preferably, the value of [(mass% CaO) + (mass% MgO)]/(mass% Al 2 O 3 ) is in a range from 1.8 to 2.5.
- the respective additive amounts are more preferably determined such that a value of (mass% MgO)/(mass% CaO) of the produced slag is equal to or smaller than 0.10.
- Those materials are added into the ladle by the determined additive amounts.
- All of the additive amount of metallic Al does not become Al 2 O 3 .
- Some amount of metallic Al is dissolved and remains in the molten steel.
- a ratio of Al 2 O 3 in slag to Al dissolved in molten steel is obtained preliminarily by an experiment.
- the additive amount of metallic Al is set on the basis of the ratio. No CaF 2 is added.
- the composition of the slag in the ladle after the desulfurization processing is adjusted to the composition that does not substantially contain CaF 2
- the slag composition of after the desulfurization processing is adjusted without using a fluorine compound such as CaF 2 as a slag formation accelerator of CaO, and even when fluorine that is unavoidably mixed into the used CaO containing material and Al 2 O 3 containing material, for example, and brought into the ladle is present in the slag after the desulfurization processing, the slag in the ladle is defined that the slag substantially does not contain CaF 2 .
- CaO containing material to be added quicklime (CaO), limestone (CaCO 3 ), slaked lime (Ca(OH) 2 ), dolomite (MgCO 3 -CaCO 3 ), and calcined dolomite (MgO-CaO) are used, for example.
- MgO containing material to be added magnesia clinker (MgO), dolomite (MgCO 3 -CaCO 3 ), and calcined dolomite (MgO-CaO) are used, for example.
- an average particle diameter of the caustic lime is in a range from 1 to 30 mm from a point of view of a reaction efficiency and an addition yield. From a point of view of reducing an amount sucked in an exhaust system, an amount of fine powder is preferably small. An amount of caustic lime having an average particle diameter equal to or larger than 30 mm is, thus, preferably small.
- the measuring method of the average particle diameter is as follows. One kilogram of a desulfurization agent was collected.
- the collected desulfurization agent was sieved into nine classes, i.e., equal to or smaller than 500 ⁇ m, 500 ⁇ m to 1 mm, 1 to 5 mm, 5 to 10 mm, 10 to 15 mm, 15 to 20 mm, 20 to 25 mm, 25 to 30 mm, and equal to or larger than 30 mm.
- Al 2 O 3 containing material aluminum dross (contains 20 to 70 mass% metallic Al and main component of the balance is Al 2 O 3 ), bauxite (Al 2 O 3 ⁇ 2H 2 O), and calcined alumina (Al 2 O 3 ) are used, for example.
- Aluminum dross can be used as alternative of metallic Al.
- SiO 2 containing material silica sand (SiO 2 ) and wollastonite (CaO-SiO 2 ) are used, for example. When the mass of the converter slag flowed in the ladle is large, the SiO 2 containing material may not be required to be added.
- the MgO containing material may not be required to be added when the slag composition satisfies that a value of [(mass% CaO) + (mass% MgO)] / (mass% Al 2 O 3 ) is in a range from 1.5 to 3.0, preferably in a range 1.8 to 2.5 without addition of the MgO containing material.
- FIG. 1 is a schematic diagram of a side view of the LF facility used when the invention is implemented.
- FIG. 1 illustrates an LF facility 1, a ladle 2, an elevating lid 3, arc heating electrodes 4, submerged lances 5 and 6, bottom-blowing porous bricks 7 and 8, molten steel 9, slag 10, a row material supply chute 11, and an Ar gas introduction pipe 12.
- the ladle 2 that contains the molten steel 9 and is mounted on a traveling carriage (not illustrated) is disposed at a certain position just under the lid 3.
- the lid 3 is moved downward to be tightly in contact with the upper end of the ladle 2.
- Ar gas is supplied from the Ar gas introduction pipe 12, resulting in a space surrounded by the ladle 2 and the lid 3 becoming Ar gas atmosphere.
- Ar gas is preferably blown from piping provided on the periphery of the furnace lid such that an oxygen concentration in the ladle 2 is equal to or smaller than 15%.
- the reduction of the oxygen concentration in the ladle 2 makes it possible to reduce an amount of Al lost by reaction with oxygen in the air in the LF processing.
- the flow rate of Ar gas blown from the ladle 2 preferably satisfies that a value of ⁇ L 2 /4Q is in a range from 50 to 150 (m/min) and more preferably 70 to 100 (m/min).
- L is the diameter (m) of the ladle and Q is the flow rate of Ar gas (Nm 3 /min).
- the flux containing those materials and metallic Al are supplied into the ladle 2 via the row material supply chute 11.
- Metallic Al is preferably added within 10 minutes after start of the desulfurization processing such that the following formula (5) is satisfied. It is, thus, preferable for promoting the desulfurization processing that metallic Al is added in accordance with the Al concentration after tapping from the converter to increase the Al concentration in molten steel. sol . Al 1 ⁇ sol . Al 2 + 0.05 ⁇ W Al ⁇ sol . Al 1 ⁇ sol .
- Al 2 + 0.1 sol Al 1 : Al concentration standard upper limit mass % in steel grade to be manufactured by being melted sol .
- Al 2 Al concentration mass % in molten steel after tapping from converter W
- Al amount kg / t of Al supplied within 10 minutes after start of ladle desulfurization processing
- the electrodes 4 are energized to generate arc, if necessary, to heat the molten steel 9 and to cause the added flux to form slag.
- the submerged lance 5 or 6 is immersed into the molten steel 9 and then Ar gas serving as a stirring gas is blown into the molten steel 9 from at least one of the submerged lances 5 and 6, or the bottom-blowing porous bricks 7 and 8 to stir the molten steel 9.
- Ar gas serving as a stirring gas is blown into the molten steel 9 from at least one of the submerged lances 5 and 6, or the bottom-blowing porous bricks 7 and 8 to stir the molten steel 9.
- the flux is mixed with the molten steel 9, thereby causing the flux to form slag.
- slag 10 is produced.
- the produced slag 10 is stirred and mixed with the molten steel 9 as a result of stirring of the molten steel 9.
- a slag-metal reaction occurs between the molten steel 9 and the slag 10 and, thus, a desulfurization reaction occurs in which sulfur in the molten steel 9 transfers into the slag.
- one or more kinds of Ca alloy powder, metallic Mg powder, and Mg alloy powder are preferably blown into the molten steel 9 together with Ar gas from the submerged lances 5 and 6, or, at least one period in the desulfurization processing, blowing of the stirring gas from the submerged lances 5 and 6 and blowing of the stirring gas from the bottom-blowing porous bricks 7 and 8 are preferably performed simultaneously.
- Ca alloy powder Ca-Si alloy powder and Ca-Al alloy powder are used, for example.
- Mg alloy powder Mg-Al-Zn alloy powder and Mg-Si-Fe alloy powder are used, for example.
- the particle diameters of those metallic powder are not limited to specific diameters as long as those metallic powder can be added by being blown. From a point of view of keeping a reaction interfacial area, the maximum particle diameter is preferably equal to or smaller than 1 mm.
- the slag composition after the desulfurization processing is adjusted such that the SiO 2 content is in a range from 5 to 15 mass% in the desulfurization processing of the molten steel 9 by the ladle refining method using the desulfurization agent containing the CaO containing material as the major constituent material.
- SiO 2 thus, functions as the slagging accelerator to promote the slag formation of CaO.
- the slag composition after the desulfurization processing is adjusted such that a value of [(mass% CaO) + (mass% MgO)]/(mass% Al 2 O 3 ) is in a range from 1.5 to 3.0, thereby causing the slag 10 to have high desulfurization ability.
- the desulfurization processing can be efficiently performed on the molten steel 9 without using CaF 2 as a part of the desulfurization agent and pre-melt flux as the desulfurization agent.
- the above description is an example where the invention is implemented using the LF facility.
- the invention can also be applied to an ASEA-SKF facility and a VAD facility according to the manner as described above.
- Molten pig iron tapped from a blast furnace was subjected to the desiliconization processing, the desulfurization processing, and the dephosphorization processing.
- the processed molten pig iron was, then, charged into a converter to be subjected to the decarburization refining.
- obtained was approximately 250 tons of molten steel having a carbon concentration ranging from 0.05 to 0.09 mass%, a sulfur concentration ranging from 0.0041 to 0.0043 mass%, and a phosphorous concentration ranging from 0.004 to 0.010 mass%.
- the converter slag flowed in a ladle was not discharged.
- Table 1 illustrates the sulfur concentrations (chemical analysis values) before and after the desulfurization processing and the desulfurization ratios in respective desulfurization tests.
- the remarks column in Table 1 illustrates "invention examples”, which are the tests according to the invention, and “comparative examples”, which are the tests other than those according to the invention.
- the desulfurization ratio is the value of a ratio of a difference in sulfur concentration in the molten steel before and after the desulfurization processing to a sulfur concentration in the molten steel before the desulfurization processing and the value is expressed by percentage.
- the desulfurization evaluation "Good” means that the sulfur concentration in the molten steel after the desulfurization processing was equal to or smaller than 0.0024% while the desulfurization evaluation "Poor” means that the sulfur concentration in the molten steel after the desulfurization processing exceeded 0.0024%.
- Table 1 also illustrates the test levels and the results.
- test numbers 1 to 3 in which the sum of volumes of pores having a pore diameter ranging from 0.5 to 10 ⁇ m is inadequate, the desulfurization ratios were lower than those in the invention examples (test numbers 4 to 15).
- test levels 4 to 15 In the invention examples having test levels in each of which the average particle diameter of quicklime is in a range from 1 to 30 mm, slag formation was promoted and the desulfurization ratio of molten steel were higher.
- Molten pig iron tapped from a blast furnace was subjected to the desiliconization processing, the desulfurization processing, and the dephosphorization processing.
- the processed molten pig iron was, then, charged into a converter to be subjected to the decarburization refining.
- obtained was approximately 250 tons of molten steel having a carbon concentration ranging from 0.05 to 0.09 mass%, a sulfur concentration ranging from 0.0041 to 0.0043 mass%, and a phosphorous concentration ranging from 0.004 to 0.010 mass%.
- the converter slag flowed in a ladle was not discharged.
- Table 2 illustrates the sulfur concentrations (chemical analysis values) before and after the desulfurization processing and the desulfurization ratios in respective desulfurization tests.
- the desulfurization evaluation "Good” means that the sulfur concentration in the molten steel after the desulfurization processing was equal to or smaller than 0.0024%.
- Table 2 also illustrates the test levels and the results. It was found that with an increase in stirring power, the slagging ratio after 5 minutes from start of the LF processing and the desulfurization ratio were increased. It was found that high slagging ratio and desulfurization ratio were obtained because the stirring power density satisfies the following formula (6).
- ⁇ stirrin g power density W / t of gas stirring molten steel
- Q gas flow rate Nm 3 / min
- W molten steel amount t
- T l molten steel temperature ° C
- T g gas temperature ° C
- h bath depth m
- P ambient pressure
- FIG. 2 is a diagram illustrating the slagging ratios of the invention examples and the comparative examples.
- Molten pig iron tapped from a blast furnace was subjected to the desiliconization processing, the desulfurization processing, and the dephosphorization processing.
- the processed molten pig iron was, then, charged into a converter to be subjected to the decarburization refining.
- obtained was approximately 250 tons of molten steel having a carbon concentration ranging from 0.05 to 0.09 mass%, a sulfur concentration ranging from 0.0041 to 0.0044 mass%, and a phosphorous concentration ranging from 0.004 to 0.010 mass%.
- the converter slag flowed in a ladle was not discharged.
- the LF processing used quicklime satisfying that the quicklime has a particle diameter equal to or smaller than 20 mm and the sum of the volumes of pores having a pore diameter ranging from 0.5 to 10 ⁇ m is 0.2 mL/g.
- Table 3 illustrates the sulfur concentrations (chemical analysis values) before and after the desulfurization processing and the desulfurization ratios in respective desulfurization tests.
- [sol.Al] 1 is the upper limit value (mass%) of an Al concentration standard of a steel grade to be manufactured by being melted and
- [sol.Al] 2 is the Al concentration (mass%) in the molten steel after tapping from the converter.
- the desulfurization evaluation "Good" means that the sulfur concentration in the molten steel after the desulfurization processing was equal to or smaller than 0.0024%.
- Molten pig iron tapped from a blast furnace was subjected to the desiliconization processing, the desulfurization processing, and the dephosphorization processing.
- the processed molten pig iron was, then, charged into a converter to be subjected to the decarburization refining.
- obtained was approximately 250 tons of molten steel having a carbon concentration ranging from 0.05 to 0.09 mass%, a sulfur concentration ranging from 0.0041 to 0.0044 mass%, and a phosphorous concentration ranging from 0.004 to 0.010 mass%.
- the converter slag flowed in a ladle was not discharged.
- the LF processing used quicklime satisfying that the quicklime has a particle diameter equal to or smaller than 20 mm and the sum of the volumes of pores having a pore diameter ranging from 0.5 to 10 ⁇ m is 0.2 mL/g.
- Metallic Al was added so as to satisfy formula (5) within 10 minutes after start of the LF processing.
- Table 4 illustrates the sulfur concentrations (chemical analysis values) before and after the desulfurization processing and the desulfurization ratios in respective desulfurization tests.
- the desulfurization evaluation "Good” means that the sulfur concentration in molten steel after the desulfurization processing was equal to or smaller than 0.0024%.
- Al 2 Al concentration mass % in molten steel after tapping from converter , sol .
- Al 3 Al concentration mass % in molten steel after completion of ladle desulfurization processing
- W A ⁇ l ⁇ - ⁇ all amount kg / t of Al supplied in ladle desulfurization processing
- X A ⁇ l ⁇ - ⁇ l ⁇ o ⁇ s ⁇ s ⁇ - ⁇ D ⁇ e ⁇ - ⁇ S amount kg / t of Al lost by desulfurization reaction 3 CaO + 3 S + 2 Al ⁇ 2 CaS + Al 2 O 3
- X A ⁇ l ⁇ - ⁇ l ⁇ o ⁇ s ⁇ s ⁇ - ⁇ slag amount kg / t of Al lost by reduction reaction 6 MnO + 4 Al ⁇ 2 Al 2 O 3 + 6 Mn , for example of oxide in slag
- X A ⁇ l ⁇ - ⁇ loss amount kg / t of Al ost by air en
- the invention can provide the desulfurization processing method of molten steel and the desulfurization agent that can efficiently perform the desulfurization processing without using CaF 2 and pre-melt flux.
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Abstract
Description
- The present invention relates to a desulfurization processing method of molten steel and a desulfurization agent.
- Recently, high purity steel manufacturing has been highly demanded for enhancing material characteristics along with adding high value to steel and an increase in use of steel materials, for example. Particularly, a demand has been highly increased for ultra low sulfur steel having a low content of sulfur, which is an element that reduces toughness of steel materials. In melting manufacturing processes of steel materials, desulfurization processing at a molten pig iron stage and desulfurization processing at a molten steel stage are available. Steel materials are typically subjected to only the desulfurization processing at the molten pig iron stage when manufactured by being melted. In the melting manufacturing processes of ultra low sulfur steel such as high-grade electromagnetic steel plates and line pipe steel materials, it is insufficient to perform only the desulfurization processing at the molten pig iron stage. It is, thus, necessary to perform the desulfurization processing at the molten steel stage in addition to the desulfurization processing at the molten pig iron stage.
- The desulfurization processing at the molten steel stage is typically performed by a ladle refining method such as an ASEA-SKF method, a VAD method, or an LF method. The ladle reining method includes an arc heating means to heat molten steel and a stirring means to stir molten steel, and further includes a blowing means to blow powder such as flux or alloy powder to molten steel. In the ladle refining method, a desulfurization agent is added into a ladle holding molten steel manufactured by being melted by decarburization refining in a converter, the molten steel and the desulfurization agent are stirred and mixed with each other or subjected to arc heating, thereby causing the desulfurization agent to form slag, and a slag-metal reaction occurs between the slag formed by slag formation of the desulfurization agent and the molten steel to transfer sulfur in the molten steel to the slag.
- The used desulfurization agent contains CaO (quicklime) as a major component and Al2O3 (alumina), CaF2 (fluorite), and the like, which are added for the purpose of lowering a melting point of the desulfurization agent. For achieving effective desulfurization reaction in the desulfurization processing method by the ladle refining method, it is important to cause the added desulfurization agent to rapidly form slag and to increase a contact area between the slag formed by the slag formation of the desulfurization agent and the metal by increasing stirring strength. The desulfurization agent is typically added to molten steel in the ladle by being placed on the molten steel. It takes a long time that the desulfurization agent forms slag in any case where the desulfurization agent forms slag by arc heating or by being stirred and mixed with the molten steel after the desulfurization agent is added.
- Patent Literature 1 discloses a method of desulfurizing molten steel in which flux, a mixture of quicklime, alumina, and fluorite, is added and bubbling processing is performed such that a slag composition after the desulfurization processing satisfies that CaO/Al2O3 ≥ 1.5 mass% and CaF2 ≥ 5 mass%.
Patent Literature 2 discloses a method in which pre-melt flux (preliminarily mixed or uniformly dissolved) of CaO-Al2O3 or pre-melt flux of CaO-Al2O3-CaF2 is used for promoting the slag formation of the desulfurization agent. As for enhancing stirring strength of molten steel,Patent Literatures -
- Patent Literature 1: Japanese Patent Application Laid-open No.
H08-260025 - Patent Literature 2: Japanese Patent Application Laid-open No.
H09-217110 - Patent Literature 3: Japanese Patent Application Laid-open No.
S61-91318 - Patent Literature 4: Japanese Patent Application Laid-open No.
S61-281809 - Patent Literature 5: Japanese Patent Application Laid-open No.
2000-234119 - The method described in Patent Literature 1, however, has a problem in that, when a desulfurization agent containing CaF2 is used, refractory forming the ladle is heavily melted and eroded by CaF2 in the produced slag, thereby significantly shortening a life-span of the ladle. The method described in
Patent Literature 2 has a problem in that the pre-melt flux is very expensive, thereby increasing processing cost. The desulfurization agent containing CaF2 has the same problem as described above. - The method described in
Patent Literatures - The invention is made in view of above problems, and aims to provide a desulfurization processing method of molten steel and a desulfurization agent that can efficiently perform desulfurization processing without using CaF2 and pre-melt flux.
- To solve the problem and achieve the object, a desulfurization processing method of molten steel according to the present invention is a method including: adding a desulfurization agent containing quicklime into a ladle holding the molten steel; and stirring the molten steel in the ladle to reduce a sulfur concentration in the molten steel, wherein the desulfurization agent contains quicklime, where a sum of volumes of pores having a pore diameter ranging from 0.5 µm to 10 µm (inclusive of 0.5 µm and 10 µm) in the quicklime is equal to or larger than 0.1 mL/g.
- Moreover, in the desulfurization processing method of molten steel according to the present invention, the quicklime contains particles, where 90% or more of the particles contained in the quicklime has a particle diameter ranging from 1 mm to 30 mm (inclusive of 1 mm and 30 mm) .
- Moreover, a desulfurization agent according to the present invention includes quicklime, where a sum of volumes of pores having a pore diameter ranging from 0.5 µm to 10 µm (inclusive of 0.5 µm and 10 µm) in the quicklime is equal to or larger than 0.1 mL/g, wherein the quicklime contains particles, where 90% or more of the particles contained in the quicklime has a particle diameter ranging from 1 mm to 30 mm (inclusive of 1 mm and 30 mm).
- Moreover, in the desulfurization processing method of molten steel according to the present invention, the stirring is performed so as to satisfy a stirring power density represented by the following formula (1). In the present specification, "Nm3" means a volume of gas at an atmospheric pressure of 101325 Pa and a temperature of 273.15 K under standard conditions.
- Moreover, in the desulfurization processing method of molten steel according to the present invention, an amount of aluminum supplied into the molten steel within 10 minutes after start of the desulfurization processing, the desulfurization processing starting after the molten steel is tapped from a converter, satisfies the following formula (2).
- Moreover, in the desulfurization processing method of molten steel according to the present invention, argon gas is blown into the ladle such that an oxygen concentration in the ladle is equal to or smaller than 15%. Advantageous Effects of Invention
- The desulfurization processing method of molten steel and the desulfurization agent according to the invention can efficiently perform desulfurization processing without using CaF2 and pre-melt flux.
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FIG. 1 is a schematic diagram of a side surface of an LF facility used when the invention is implemented. -
FIG. 2 is a diagram illustrating slagging ratios in invention examples and comparative examples. - The inventors of the invention have earnestly studied for solving the problems described above by focusing attention on a particle size and a pore diameter of caustic lime and molten steel components. More specifically, the inventors of the invention have performed various experiments and researches for the purpose of causing flux added as a desulfurization agent to rapidly form slag to achieve efficient desulfurization processing without using CaF2 as a part of the desulfurization agent when low sulfur steel having a sulfur concentration equal to or smaller than 0.0030 mass% is manufactured by being melted by desulfurization processing by a ladle refining method using a desulfurization agent having a CaO containing material as a major constituent material.
- As a result, the inventors of the invention have found that the temperature of molten steel when flux is added, a sol. Al concentration, and the particle size and the pore diameter of caustic lime are important in order to promote flux added as a desulfurization agent to form slag. The temperature of molten steel is determined by the temperature of molten steel when the molten steel is tapped from a converter. As the temperature of the molten steel when the molten steel is tapped is increased, the refractory of the converter is increasingly melted and eroded, thereby causing processing cost to be increased. An immoderate increase in tapping temperature is, thus, inadvisable.
- The inventors of the invention have found that the desulfurization processing can be performed highly efficiently using a powder desulfurization agent containing quicklime as a major component and the quicklime satisfies that a sum of volumes of pores having a pore diameter ranging from 0.5 to 10 µm in all of the pores included in the quicklime is equal to or larger than 0.1 mL/g. The inventors of the invention, thus, have conceived the invention. The pore diameter distribution of quicklime was measured by the following method.
- As pretreatment, quicklime was dried at a constant temperature of 120 °C for 4 hours. Using Micromerities autopore IV 9520, a pore diameter distribution of dried quicklime having a pore diameter ranging from approximately 0.0036 to 200 µm was obtained by a mercury intrusion method, and a cumulative pore volume curve was calculated. In addition, a sum of volumes of pores having a pore diameter ranging from 0.5 to 10 µm was obtained from the calculated cumulative pore volume curve.
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- Molten pig iron tapped from a blast furnace is received by a hot metal transfer vessel such as a hot metal ladle or a torpedo car, and transferred to a converter in which decarburization refining is performed as the next process. Typically, during the transportation, hot metal pretreatment such as desulfurization processing and dephosphorization processing are performed on molten pig iron. The invention is the technique to manufacture low sulfur steel. The desulfurization processing is, thus, performed. Even when the dephosphorization processing is not required in accordance with the compositional standard of the low sulfur steel, the dephosphorization processing is performed to prevent rephosphorization from converter slag in desulfurization processing after tapping from the converter.
- The decarburization refining is performed on the molten pig iron on which the desulfurization processing and the dephosphorization processing are performed, and resulting molten steel is tapped to the ladle. In the decarburization refining in the converter, a little amount of quicklime (CaO) and a little amount of dolomite (MgCO3-CaCO3), or calcined dolomite (MgO-CaO) is used as flux, and the flux forms slag in the converter (hereinafter described as the "converter slag"), because the desulfurization processing and the dephosphorization processing are already performed on the molten pig iron. The converter slag has a role to promote dephosphorization reaction of the molten pig iron. The dephosphorization processing is, however, already performed on the molten pig iron. The main role of converter slag is, thus, prevention of occurrence of iron splashes in blowing refining and melting and erosion of the lining refractory of the converter.
- At the last stage of tapping, the converter slag is mixed into the molten steel and flows into the ladle. Slag flow-out prevention measures, which are typically taken, are performed to prevent the flow out of the converter slag. It is, however, difficult to perfectly prevent the converter slag from being flowed out even when the slag flow-out prevention measures are taken. Some amount of converter slag is mixed into the molten steel in the ladle and flows out from the converter. After tapping, the converter slag that is mixed into the molten steel and flows into the ladle may be removed from the ladle. The converter slag may, however, not be removed because SiO2 component in the converter slag contributes to the slag formation of a CaO containing material added later as the desulfurization agent.
- In order to form CaO-MgO-Al2O3-SiO2 desulfurization slag having a certain composition in the ladle, a CaO containing material, a MgO containing material, an Al2O3 containing material, and a SiO2 containing material are added into the ladle as flux. As described above, MgO has a lower desulfurization ability than that of CaO, the MgO containing material may not be added. Metallic Al is added into the ladle for deoxidation of the molten steel and reduction of the slag (reduction of Fe oxides and Mn oxides in the slag).
- Those materials may be added into a facility in later process that performs desulfurization processing by any of an ASEA-SKF method, a VAD method, and an LF method. From a point of view of promoting the slag formation of CaO, those materials are preferably added into the ladle at tapping from the converter to the ladle or just after the tapping. It is preferable for quicklime added just after the tapping that a sum of volumes of pores having a pore diameter ranging from 0.5 to 10 µm in all of the pores included in the quicklime is equal to or larger than 0.1 mL/g, and the quicklime contains particles 90% or more of which have a particle diameter ranging from 1 to 30 mm.
- Respective additive amounts of the CaO containing material, the MgO containing material, metallic Al, the Al2O3 containing material, and the SiO2 containing material are determined, by considering a mass and a component composition of converter slag flowed into the ladle, such that the composition of the slag produced in the ladle after the slag formation of the added flux, i.e., the slag formed from the flux and the converter slag, satisfies that the SiO2 content is in a range from 5 to 15 mass% and a value of [(mass% CaO) + (mass% MgO)]/(mass% Al2O3) is in a range from 1.5 to 3.0, and, preferably, the value of [(mass% CaO) + (mass% MgO)]/(mass% Al2O3) is in a range from 1.8 to 2.5.
- In this case, the respective additive amounts are more preferably determined such that a value of (mass% MgO)/(mass% CaO) of the produced slag is equal to or smaller than 0.10. Those materials are added into the ladle by the determined additive amounts. All of the additive amount of metallic Al does not become Al2O3. Some amount of metallic Al is dissolved and remains in the molten steel. A ratio of Al2O3 in slag to Al dissolved in molten steel is obtained preliminarily by an experiment. The additive amount of metallic Al is set on the basis of the ratio. No CaF2 is added.
- In the invention, "the composition of the slag in the ladle after the desulfurization processing is adjusted to the composition that does not substantially contain CaF2" means that the slag composition of after the desulfurization processing is adjusted without using a fluorine compound such as CaF2 as a slag formation accelerator of CaO, and even when fluorine that is unavoidably mixed into the used CaO containing material and Al2O3 containing material, for example, and brought into the ladle is present in the slag after the desulfurization processing, the slag in the ladle is defined that the slag substantially does not contain CaF2.
- As for the CaO containing material to be added, quicklime (CaO), limestone (CaCO3), slaked lime (Ca(OH)2), dolomite (MgCO3-CaCO3), and calcined dolomite (MgO-CaO) are used, for example. As for the MgO containing material to be added, magnesia clinker (MgO), dolomite (MgCO3-CaCO3), and calcined dolomite (MgO-CaO) are used, for example.
- It is preferable for a particle size of caustic lime that an average particle diameter of the caustic lime is in a range from 1 to 30 mm from a point of view of a reaction efficiency and an addition yield. From a point of view of reducing an amount sucked in an exhaust system, an amount of fine powder is preferably small. An amount of caustic lime having an average particle diameter equal to or larger than 30 mm is, thus, preferably small. The measuring method of the average particle diameter is as follows. One kilogram of a desulfurization agent was collected. The collected desulfurization agent was sieved into nine classes, i.e., equal to or smaller than 500 µm, 500 µm to 1 mm, 1 to 5 mm, 5 to 10 mm, 10 to 15 mm, 15 to 20 mm, 20 to 25 mm, 25 to 30 mm, and equal to or larger than 30 mm. The average particle diameter was obtained by calculating the weight ratio represented in the following formula (4).
- As for the Al2O3 containing material, aluminum dross (contains 20 to 70 mass% metallic Al and main component of the balance is Al2O3), bauxite (Al2O3·2H2O), and calcined alumina (Al2O3) are used, for example. Aluminum dross can be used as alternative of metallic Al. As for the SiO2 containing material, silica sand (SiO2) and wollastonite (CaO-SiO2) are used, for example. When the mass of the converter slag flowed in the ladle is large, the SiO2 containing material may not be required to be added. The MgO containing material may not be required to be added when the slag composition satisfies that a value of [(mass% CaO) + (mass% MgO)] / (mass% Al2O3) is in a range from 1.5 to 3.0, preferably in a range 1.8 to 2.5 without addition of the MgO containing material.
- The ladle holding the molten steel is transferred to the facility that performs the desulfurization processing by any of the ASEA-SKF method, the VAD method, and the LF method, and the desulfurization processing is performed on the molten steel by the facility. In the invention, the desulfurization processing is performed by an LF facility as an example.
FIG. 1 is a schematic diagram of a side view of the LF facility used when the invention is implemented.FIG. 1 illustrates an LF facility 1, aladle 2, an elevatinglid 3,arc heating electrodes 4, submergedlances porous bricks slag 10, a rowmaterial supply chute 11, and an Argas introduction pipe 12. - In the LF facility 1, the
ladle 2 that contains the molten steel 9 and is mounted on a traveling carriage (not illustrated) is disposed at a certain position just under thelid 3. Thelid 3 is moved downward to be tightly in contact with the upper end of theladle 2. While the contact is kept, Ar gas is supplied from the Argas introduction pipe 12, resulting in a space surrounded by theladle 2 and thelid 3 becoming Ar gas atmosphere. Ar gas is preferably blown from piping provided on the periphery of the furnace lid such that an oxygen concentration in theladle 2 is equal to or smaller than 15%. The reduction of the oxygen concentration in theladle 2 makes it possible to reduce an amount of Al lost by reaction with oxygen in the air in the LF processing. The flow rate of Ar gas blown from theladle 2 preferably satisfies that a value of πL2/4Q is in a range from 50 to 150 (m/min) and more preferably 70 to 100 (m/min). L is the diameter (m) of the ladle and Q is the flow rate of Ar gas (Nm3/min). When the flow rate of Ar gas is small, the oxygen concentration is not sufficiently reduced. In contrast, when the flow rate of Ar gas is too large, the molten steel temperature is caused to be reduced. - When the CaO containing material, the MgO containing material, metallic Al, the Al2O3 containing material, and the SiO2 containing material are not preliminarily added into the
ladle 2, and when the additive amounts of those materials are insufficient, the flux containing those materials and metallic Al are supplied into theladle 2 via the rowmaterial supply chute 11. Metallic Al is preferably added within 10 minutes after start of the desulfurization processing such that the following formula (5) is satisfied. It is, thus, preferable for promoting the desulfurization processing that metallic Al is added in accordance with the Al concentration after tapping from the converter to increase the Al concentration in molten steel. - Then, the
electrodes 4 are energized to generate arc, if necessary, to heat the molten steel 9 and to cause the added flux to form slag. Thereafter, the submergedlance lances porous bricks slag 10 is produced. - The produced
slag 10 is stirred and mixed with the molten steel 9 as a result of stirring of the molten steel 9. As a result, a slag-metal reaction occurs between the molten steel 9 and theslag 10 and, thus, a desulfurization reaction occurs in which sulfur in the molten steel 9 transfers into the slag. From a point of view of promoting the desulfurization reaction, as described above, one or more kinds of Ca alloy powder, metallic Mg powder, and Mg alloy powder are preferably blown into the molten steel 9 together with Ar gas from the submergedlances lances porous bricks - As for the Ca alloy powder, Ca-Si alloy powder and Ca-Al alloy powder are used, for example. As for the Mg alloy powder, Mg-Al-Zn alloy powder and Mg-Si-Fe alloy powder are used, for example. The particle diameters of those metallic powder are not limited to specific diameters as long as those metallic powder can be added by being blown. From a point of view of keeping a reaction interfacial area, the maximum particle diameter is preferably equal to or smaller than 1 mm. When the sulfur concentration in the molten steel 9 becomes equal to or smaller than 0.0010 mass%, blowing Ar gas into the molten steel 9 stops to end the desulfurization processing. When the temperature of the molten steel 9 is lower than a target temperature at the end of the desulfurization processing, arc heating is performed. When the composition of the molten steel 9 is not in a target range, an alloy iron and metals for composition adjustment are supplied via the row
material supply chute 11. After the completion of the desulfurization processing, degassing refining is performed by an RH vacuum degassing apparatus, for example. Thereafter, a strip cast slab is casted by a continuous casting machine. - As described above, in the invention, the slag composition after the desulfurization processing is adjusted such that the SiO2 content is in a range from 5 to 15 mass% in the desulfurization processing of the molten steel 9 by the ladle refining method using the desulfurization agent containing the CaO containing material as the major constituent material. SiO2, thus, functions as the slagging accelerator to promote the slag formation of CaO. In addition, the slag composition after the desulfurization processing is adjusted such that a value of [(mass% CaO) + (mass% MgO)]/(mass% Al2O3) is in a range from 1.5 to 3.0, thereby causing the
slag 10 to have high desulfurization ability. As a result, the desulfurization processing can be efficiently performed on the molten steel 9 without using CaF2 as a part of the desulfurization agent and pre-melt flux as the desulfurization agent. The above description is an example where the invention is implemented using the LF facility. The invention can also be applied to an ASEA-SKF facility and a VAD facility according to the manner as described above. - Molten pig iron tapped from a blast furnace was subjected to the desiliconization processing, the desulfurization processing, and the dephosphorization processing. The processed molten pig iron was, then, charged into a converter to be subjected to the decarburization refining. As a result, obtained was approximately 250 tons of molten steel having a carbon concentration ranging from 0.05 to 0.09 mass%, a sulfur concentration ranging from 0.0041 to 0.0043 mass%, and a phosphorous concentration ranging from 0.004 to 0.010 mass%. After tapping, the converter slag flowed in a ladle was not discharged. Metallic Al, quicklime, lightly calcined dolomite, and aluminum dross were added into the ladle, and the ladle was transferred to the LF facility illustrated in
FIG. 1 . The desulfurization processing was performed for approximately 30 minutes in such a manner that the molten steel was stirred by blowing Ar gas at 2000 NL/min from the submerged lances into the molten steel while the arc heating was performed by the electrodes immersed in the slag so as to achieve a target sulfur concentration equal to or smaller than 0.0024%. - Table 1 illustrates the sulfur concentrations (chemical analysis values) before and after the desulfurization processing and the desulfurization ratios in respective desulfurization tests. The remarks column in Table 1 illustrates "invention examples", which are the tests according to the invention, and "comparative examples", which are the tests other than those according to the invention. The desulfurization ratio is the value of a ratio of a difference in sulfur concentration in the molten steel before and after the desulfurization processing to a sulfur concentration in the molten steel before the desulfurization processing and the value is expressed by percentage. The desulfurization evaluation "Good" means that the sulfur concentration in the molten steel after the desulfurization processing was equal to or smaller than 0.0024% while the desulfurization evaluation "Poor" means that the sulfur concentration in the molten steel after the desulfurization processing exceeded 0.0024%.
Table 1 Test No. Sum of volumes of pores 0.5-10 µm Average particle diameter [S] Component change Desulfurization evaluation Remarks Before processing [S] After processing [S] Desulfurization ratio mL/g mm Mass [%] Mass [%] [%] - 1 0.03 10 0.0042 0.0028 33.3 Poor Comparative example 2 0.06 10 0.0043 0.0027 37.2 Poor Comparative example 3 0.09 10 0.0041 0.0025 39.0 Poor Comparative example 4 0.15 10 0.0042 0.0021 50.0 Good Example 5 0.2 10 0.0042 0.0019 54.8 Good Example 6 0.2 0.5 0.0044 0.0022 50.0 Good Example 7 0.2 0.8 0.0041 0.0020 51.2 Good Example 8 0.2 1.5 0.0043 0.0018 58.1 Good Example 9 0.2 3 0.0043 0.0016 62.8 Good Example 10 0.2 5 0.0042 0.0016 61.9 Good Example 11 0.2 15 0.0041 0.0015 63.4 Good Example 12 0.2 25 0.0043 0.0014 67.4 Good Example 13 0.2 28 0.0042 0.0016 61.9 Good Example 14 0.2 32 0.0043 0.0017 60.5 Good Example 15 0.2 40 0.0042 0.0019 54.8 Good Example - Table 1 also illustrates the test levels and the results. In the comparative examples (test numbers 1 to 3), in which the sum of volumes of pores having a pore diameter ranging from 0.5 to 10 µm is inadequate, the desulfurization ratios were lower than those in the invention examples (
test numbers 4 to 15). In the invention examples having test levels in each of which the average particle diameter of quicklime is in a range from 1 to 30 mm, slag formation was promoted and the desulfurization ratio of molten steel were higher. - Molten pig iron tapped from a blast furnace was subjected to the desiliconization processing, the desulfurization processing, and the dephosphorization processing. The processed molten pig iron was, then, charged into a converter to be subjected to the decarburization refining. As a result, obtained was approximately 250 tons of molten steel having a carbon concentration ranging from 0.05 to 0.09 mass%, a sulfur concentration ranging from 0.0041 to 0.0043 mass%, and a phosphorous concentration ranging from 0.004 to 0.010 mass%. After tapping, the converter slag flowed in a ladle was not discharged. Metallic Al, quicklime, lightly calcined dolomite, and aluminum dross were added into the ladle, and the ladle was transferred to the LF facility illustrated in
FIG. 1 . The desulfurization processing was performed for approximately 30 minutes in such a manner that the molten steel was stirred by blowing Ar gas at 500 to 2000 NL/min from the submerged lances into the molten steel while the arc heating was performed by the electrodes immersed in the slag so as to achieve a target sulfur concentration equal to or smaller than 0.0024%. - Table 2 illustrates the sulfur concentrations (chemical analysis values) before and after the desulfurization processing and the desulfurization ratios in respective desulfurization tests. The desulfurization evaluation "Good" means that the sulfur concentration in the molten steel after the desulfurization processing was equal to or smaller than 0.0024%.
Table 2 Test No. Stirring power density Slagging ratio 5 min. after start of LF processing [S] Component change Desulfurization evaluation Remarks Before processing [S] After processing [S] Desulfurization ratio [W/t] [%] Mass [%] Mass [%] [%] - - 16 10 35 0.0042 0.0019 54.8 Good Example 17 15 50 0.0042 0.0018 57.1 Good Example 18 27 57 0.0041 0.0018 56.1 Good Example 19 35 68 0.0042 0.0018 57.1 Good Example 20 45 85 0.0042 0.0017 59.5 Good Example 21 55 94 0.0042 0.0017 59.5 Good Example 22 74 100 0.0042 0.0017 59.5 Good Example 23 100 100 0.0043 0.0015 65.1 Good Example 24 135 100 0.0041 0.0014 65.9 Good Example 25 158 100 0.0042 0.0013 69.0 Good Example 26 167 100 0.0042 0.0012 71.4 Good Example 27 185 100 0.0044 0.0011 75.0 Good Example - Table 2 also illustrates the test levels and the results. It was found that with an increase in stirring power, the slagging ratio after 5 minutes from start of the LF processing and the desulfurization ratio were increased. It was found that high slagging ratio and desulfurization ratio were obtained because the stirring power density satisfies the following formula (6).
-
FIG. 2 is a diagram illustrating the slagging ratios of the invention examples and the comparative examples. The invention examples used quicklime satisfying that the quicklime has a particle diameter equal to or smaller than 20 mm and the sum of the volumes of pores having a pore diameter ranging from 0.5 to 10 µm is 0.2 mL/g. The comparative examples used quicklime satisfying that the quicklime has a particle diameter equal to or smaller than 20 mm and the sum of the volumes of pores having a pore diameter ranging from 0.5 to 10 µm is 0.03 mL/g. As illustrated inFIG. 2 , it was found that slagging was more promoted in the invention examples than that in the comparative examples even at the identical stirring power density (135 W/t). - Molten pig iron tapped from a blast furnace was subjected to the desiliconization processing, the desulfurization processing, and the dephosphorization processing. The processed molten pig iron was, then, charged into a converter to be subjected to the decarburization refining. As a result, obtained was approximately 250 tons of molten steel having a carbon concentration ranging from 0.05 to 0.09 mass%, a sulfur concentration ranging from 0.0041 to 0.0044 mass%, and a phosphorous concentration ranging from 0.004 to 0.010 mass%. After tapping, the converter slag flowed in a ladle was not discharged. Metallic Al, quicklime, lightly calcined dolomite, and aluminum dross were added into the ladle, and the ladle was transferred to the LF facility illustrated in
FIG. 1 . The LF processing used quicklime satisfying that the quicklime has a particle diameter equal to or smaller than 20 mm and the sum of the volumes of pores having a pore diameter ranging from 0.5 to 10 µm is 0.2 mL/g. - Table 3 illustrates the sulfur concentrations (chemical analysis values) before and after the desulfurization processing and the desulfurization ratios in respective desulfurization tests. [sol.Al]1 is the upper limit value (mass%) of an Al concentration standard of a steel grade to be manufactured by being melted and [sol.Al]2 is the Al concentration (mass%) in the molten steel after tapping from the converter. The desulfurization evaluation "Good" means that the sulfur concentration in the molten steel after the desulfurization processing was equal to or smaller than 0.0024%.
Table 3 Test No. [sol.Al]1 [sol.Al]2 Left side of Formula (5) Right side of Formula (5) WAl [sol.Al]3 RH processing time [S] Component change Desulfurization evaluation Remarks Before processing [S] After processing [S] Desulfurization ratic % % kg/t kg/t kg/t % min Mass [%] Mass [%] [%] - 28 0.050 0.023 0.77 1.27 1 0.039 30 0.0042 0.0011 73.8 Good Example 29 0.050 0.025 0.75 1.25 1.1 0.043 29 0.0043 0.0011 74.4 Good Example 30 0.050 0.026 0.74 1.24 1.2 0.047 31 0.0041 0.0010 75.6 Good Example 31 0.050 0.024 0.76 1.26 1.3 0.051 36 0.0042 0.0009 78.6 Good Example 32 0.050 0.025 0.75 1.25 1.4 0.055 39 0.0042 0.0008 81.0 Good Example 33 0.050 0.024 0.76 1.26 1.5 0.059 42 0.0044 0.0008 81.8 Good Example - As illustrated in Table 3, in the test levels in which the amount of Al supplied within 10 minutes after start of the LF processing is in the range represented by formula (5), the value of [sol.Al]3 at the end of the LF processing was within the standard and the desulfurization ratio was higher. In the test levels in which the amount of Al supplied within 10 minutes after start of the LF processing was larger than the range represented by formula (5), the value of [sol.Al]3 at the end of the LF processing exceeded the upper limit value of the standard. Dealuminization was, thus, necessary in the next process RH and the processing time in the RH was, thus, extended.
- Molten pig iron tapped from a blast furnace was subjected to the desiliconization processing, the desulfurization processing, and the dephosphorization processing. The processed molten pig iron was, then, charged into a converter to be subjected to the decarburization refining. As a result, obtained was approximately 250 tons of molten steel having a carbon concentration ranging from 0.05 to 0.09 mass%, a sulfur concentration ranging from 0.0041 to 0.0044 mass%, and a phosphorous concentration ranging from 0.004 to 0.010 mass%. After tapping, the converter slag flowed in a ladle was not discharged. Metallic Al, quicklime, lightly calcined dolomite, and aluminum dross were added into the ladle, and the ladle was transferred to the LF facility illustrated in
FIG. 1 . The LF processing used quicklime satisfying that the quicklime has a particle diameter equal to or smaller than 20 mm and the sum of the volumes of pores having a pore diameter ranging from 0.5 to 10 µm is 0.2 mL/g. Metallic Al was added so as to satisfy formula (5) within 10 minutes after start of the LF processing. - Table 4 illustrates the sulfur concentrations (chemical analysis values) before and after the desulfurization processing and the desulfurization ratios in respective desulfurization tests. The desulfurization evaluation "Good" means that the sulfur concentration in molten steel after the desulfurization processing was equal to or smaller than 0.0024%.
Table 4 Test No. Oxygen concentration Al loss in processing (Air entrainment) [S] Component change Desulfurization evaluation Remarks Before Processing [S] After Processing [S] Desulfurization ratio - % kg/t Mass [%] Mass [%] [%] - 34 20 0.50 0.0042 0.0014 66.7 Good Example 35 18 0.47 0.0043 0.0014 67.4 Good Example 36 16 0.45 0.0041 0.0013 68.3 Good Example 37 14 0.37 0.0042 0.0012 71.4 Good Example 38 12 0.32 0.0042 0.0011 73.8 Good Example 39 10 0.30 0.0044 0.0010 77.3 Good Example -
- The invention can provide the desulfurization processing method of molten steel and the desulfurization agent that can efficiently perform the desulfurization processing without using CaF2 and pre-melt flux. Reference Signs List
-
- 1
- LF facility
- 2
- ladle
- 3
- lid
- 4
- electrode
- 5, 6
- submerged lance
- 7, 8
- bottom-blowing porous brick
- 9
- molten steel
- 10
- slag
- 11
- row material supply chute
- 12
- Ar gas introduction pipe
Claims (6)
- A desulfurization processing method of molten steel, comprising:adding a desulfurization agent containing quicklime into a ladle holding the molten steel; andstirring the molten steel in the ladle to reduce a sulfur concentration in the molten steel, whereinthe desulfurization agent contains quicklime, where a sum of volumes of pores having a pore diameter ranging from 0.5 µm to 10 µm (inclusive of 0.5 µm and 10 µm) in the quicklime is equal to or larger than 0.1 mL/g.
- The desulfurization processing method of molten steel according to claim 1, wherein the quicklime contains particles, where 90% or more of the particles contained in the quicklime has a particle diameter ranging from 1 mm to 30 mm (inclusive of 1 mm and 30 mm).
- A desulfurization agent comprising quicklime, where a sum of volumes of pores having a pore diameter ranging from 0.5 µm to 10 µm (inclusive of 0.5 µm and 10 µm) in the quicklime is equal to or larger than 0.1 mL/g, wherein the quicklime contains particles, where 90% or more of the particles contained in the quicklime has a particle diameter ranging from 1 mm to 30 mm (inclusive of 1 mm and 30 mm) .
- The desulfurization processing method of molten steel according to any one of claims 1, 2, and 4, wherein an amount of aluminum supplied into the molten steel within 10 minutes after start of the desulfurization processing, the desulfurization processing starting after the molten steel is tapped from a converter, satisfies the following formula (2) :
- The desulfurization processing method of molten steel according to any one of claims 1, 2, 4, and 5, wherein argon gas is blown into the ladle such that an oxygen concentration in the ladle is equal to or smaller than 15%.
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CN110315064A (en) * | 2019-06-20 | 2019-10-11 | 同济大学 | A kind of raw metal purification process agent and purification treating method |
CN111621620A (en) * | 2020-06-03 | 2020-09-04 | 马鞍山市兴达冶金新材料有限公司 | Desulfurization process for improving desulfurization efficiency |
CN112939042A (en) * | 2021-01-29 | 2021-06-11 | 重庆坤垠环保科技实业发展有限公司 | Method and device for cooperatively treating and utilizing aluminum ash and silica fume |
TWI762226B (en) * | 2021-03-05 | 2022-04-21 | 國立中興大學 | Preparation method of desulfurizer for steelmaking |
CN113088612A (en) * | 2021-03-15 | 2021-07-09 | 石家庄钢铁有限责任公司 | Method for pretreating and desulfurizing molten iron by using LF (ladle furnace) |
CN113832296B (en) * | 2021-09-30 | 2022-10-14 | 广东韶钢松山股份有限公司 | Rapid desulfurization method of slab steel in LF refining furnace |
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JPS6256509A (en) * | 1985-09-04 | 1987-03-12 | Kawasaki Steel Corp | Method for desulfurizing molten iron by using quicklime |
JPH0645485B2 (en) * | 1986-05-29 | 1994-06-15 | 川崎製鉄株式会社 | Method for producing quicklime for refining agent having excellent reactivity |
JPH08260025A (en) | 1995-03-24 | 1996-10-08 | Sumitomo Metal Ind Ltd | Production of extra low-sulfur and extra low oxygen steel |
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JPH11221432A (en) * | 1998-02-04 | 1999-08-17 | Nittetsu Mining Co Ltd | Limestone type desulfurization agent and production of desulfurization agent |
JP2000234119A (en) | 1999-02-09 | 2000-08-29 | Kawasaki Steel Corp | Method for desulfurizing steel |
JP2004225059A (en) * | 2002-11-28 | 2004-08-12 | Nippon Steel Corp | Method for desulfurizing molten pig iron |
JP5343308B2 (en) * | 2006-09-11 | 2013-11-13 | Jfeスチール株式会社 | Desulfurization method for molten steel |
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JP5195833B2 (en) * | 2009-06-30 | 2013-05-15 | Jfeスチール株式会社 | Hot metal desulfurization method |
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