EP3572534A1 - Procédé de traitement de désulfuration destiné à de l'acier fondu, et agent de désulfuration - Google Patents

Procédé de traitement de désulfuration destiné à de l'acier fondu, et agent de désulfuration Download PDF

Info

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
Application number
EP18741544.3A
Other languages
German (de)
English (en)
Other versions
EP3572534A4 (fr
EP3572534B1 (fr
Inventor
Yusuke Fujii
Yoshie Nakai
Hideya Masaki
Naoki Kikuchi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Steel Corp
Original Assignee
JFE Steel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=62908427&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP3572534(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by JFE Steel Corp filed Critical JFE Steel Corp
Publication of EP3572534A4 publication Critical patent/EP3572534A4/fr
Publication of EP3572534A1 publication Critical patent/EP3572534A1/fr
Application granted granted Critical
Publication of EP3572534B1 publication Critical patent/EP3572534B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
EP18741544.3A 2017-01-19 2018-01-10 Procede de traitement de désulfuration d'acier fondu et agent de désulfuration Active EP3572534B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017007209 2017-01-19
PCT/JP2018/000280 WO2018135344A1 (fr) 2017-01-19 2018-01-10 Procédé de traitement de désulfuration destiné à de l'acier fondu, et agent de désulfuration

Publications (3)

Publication Number Publication Date
EP3572534A4 EP3572534A4 (fr) 2019-11-27
EP3572534A1 true EP3572534A1 (fr) 2019-11-27
EP3572534B1 EP3572534B1 (fr) 2021-04-28

Family

ID=62908427

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18741544.3A Active EP3572534B1 (fr) 2017-01-19 2018-01-10 Procede de traitement de désulfuration d'acier fondu et agent de désulfuration

Country Status (7)

Country Link
EP (1) EP3572534B1 (fr)
JP (1) JP6743915B2 (fr)
KR (1) KR102290861B1 (fr)
CN (1) CN110177889B (fr)
BR (1) BR112019013592B1 (fr)
TW (1) TWI660049B (fr)
WO (1) WO2018135344A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI704232B (zh) * 2019-04-11 2020-09-11 日商日本製鐵股份有限公司 高效率的熔融鐵合金之精煉方法
CN110315064A (zh) * 2019-06-20 2019-10-11 同济大学 一种金属原料纯化处理剂以及纯化处理方法
CN111621620A (zh) * 2020-06-03 2020-09-04 马鞍山市兴达冶金新材料有限公司 一种提高脱硫效率的脱硫工艺
CN112939042A (zh) * 2021-01-29 2021-06-11 重庆坤垠环保科技实业发展有限公司 铝灰渣与硅灰协同处理利用方法及装置
TWI762226B (zh) * 2021-03-05 2022-04-21 國立中興大學 煉鋼用脫硫劑的製備方法
CN113088612A (zh) * 2021-03-15 2021-07-09 石家庄钢铁有限责任公司 利用lf炉进行铁水预处理脱硫的方法
CN113832296B (zh) * 2021-09-30 2022-10-14 广东韶钢松山股份有限公司 一种板坯钢在lf精炼炉内的快速脱硫方法
TWI820759B (zh) * 2022-06-20 2023-11-01 興展技術開發股份有限公司 鋼液脫硫方法

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6191318A (ja) 1984-10-12 1986-05-09 Nippon Kokan Kk <Nkk> 取鍋精錬炉の操業方法
JPS61281809A (ja) 1985-06-06 1986-12-12 Nippon Steel Corp 溶鋼の取鍋精錬法
JPS6256509A (ja) * 1985-09-04 1987-03-12 Kawasaki Steel Corp 生石灰を用いる溶銑脱硫方法
JPH0645485B2 (ja) * 1986-05-29 1994-06-15 川崎製鉄株式会社 反応性に優れた精錬剤用の生石灰の製造方法
JPH08260025A (ja) 1995-03-24 1996-10-08 Sumitomo Metal Ind Ltd 極低硫極低酸素鋼の製造方法
JPH09217110A (ja) 1996-02-14 1997-08-19 Sumitomo Metal Ind Ltd 超低硫鋼の溶製方法
JPH11221432A (ja) * 1998-02-04 1999-08-17 Nittetsu Mining Co Ltd 石灰石系脱硫剤およびその製造方法
JP2000234119A (ja) 1999-02-09 2000-08-29 Kawasaki Steel Corp 鋼の脱硫方法
JP2004225059A (ja) * 2002-11-28 2004-08-12 Nippon Steel Corp 溶銑の脱硫方法
JP5343308B2 (ja) * 2006-09-11 2013-11-13 Ｊｆｅスチール株式会社 溶鋼の脱硫方法
JP5101988B2 (ja) * 2007-10-26 2012-12-19 新日鐵住金株式会社 溶融金属の脱硫剤
JP4445564B2 (ja) * 2008-09-05 2010-04-07 新日本製鐵株式会社 溶銑の脱硫方法
KR101366720B1 (ko) * 2009-06-30 2014-02-24 제이에프이 스틸 가부시키가이샤 용선의 탈황 방법
JP5333536B2 (ja) * 2011-07-22 2013-11-06 新日鐵住金株式会社 高清浄度軸受鋼およびその溶製方法
CN102337370B (zh) * 2011-10-26 2013-05-01 辽宁博联特冶金科技有限公司 一种冶炼工业纯铁的装置及方法
CN102517418B (zh) * 2011-12-12 2013-06-05 中北大学 一种多孔颗粒状低碳石灰及其生产方法
JP6451363B2 (ja) * 2015-02-04 2019-01-16 新日鐵住金株式会社 溶鋼の脱硫方法
EP3327150B1 (fr) * 2015-07-24 2019-12-25 JFE Steel Corporation Agent de désulfuration, procédé de désulfuration de la fonte en fusion et procédé permettant de produire de la fonte en fusion
JP6402762B2 (ja) * 2015-10-05 2018-10-10 Ｊｆｅスチール株式会社 脱硫剤、機械攪拌式溶銑脱硫方法及び脱硫溶銑の製造方法
JP6369516B2 (ja) * 2015-10-05 2018-08-08 Ｊｆｅスチール株式会社 機械攪拌式溶銑脱硫方法
CN105274272A (zh) * 2015-11-27 2016-01-27 马鞍山钢铁股份有限公司 一种复合喷吹铁水脱硫材料及其调节装置

Also Published As

Publication number Publication date
EP3572534A4 (fr) 2019-11-27
WO2018135344A1 (fr) 2018-07-26
TWI660049B (zh) 2019-05-21
JPWO2018135344A1 (ja) 2019-06-27
JP6743915B2 (ja) 2020-08-19
CN110177889A (zh) 2019-08-27
KR20190108136A (ko) 2019-09-23
CN110177889B (zh) 2021-06-11
BR112019013592B1 (pt) 2022-08-16
BR112019013592A2 (pt) 2020-01-07
EP3572534B1 (fr) 2021-04-28
KR102290861B1 (ko) 2021-08-17
TW201829790A (zh) 2018-08-16

Similar Documents

Publication Publication Date Title
EP3572534B1 (fr) Procede de traitement de désulfuration d&#39;acier fondu et agent de désulfuration
RU2765475C1 (ru) Способ производства кислотоустойчивой трубопроводной стали высокой чистоты
JP5573424B2 (ja) 溶鋼の脱硫処理方法
JP2013234379A (ja) 極低燐極低硫鋼の溶製方法
CN113061799A (zh) 高洁净度弹簧钢及其生产方法
JP7060113B2 (ja) 溶鋼へのＣａ添加方法
JP6028755B2 (ja) 低硫鋼の溶製方法
JP4464343B2 (ja) アルミキルド鋼の製造方法
JP5895887B2 (ja) 溶鋼の脱硫処理方法
JP5891826B2 (ja) 溶鋼の脱硫方法
CN114457204B (zh) 铁水的脱磷方法
JP2018100427A (ja) 低硫鋼の製造方法
JP2008169407A (ja) 溶鋼の脱硫方法
JP4360270B2 (ja) 溶鋼の精錬方法
JP2007092159A (ja) 清浄性に優れた極低炭素鋼の製造方法
JP6658049B2 (ja) 溶銑の脱珪処理方法
CN115820981B (zh) 一种减少铝脱氧钢中含硅大尺寸夹杂物的冶炼工艺
JP4360239B2 (ja) 真空脱ガス設備における溶鋼の脱硫処理方法
JP2000038614A (ja) 清浄性に優れた極低炭素鋼の溶製方法
JP2009173994A (ja) Ａｌレス極低炭素鋼の溶製方法
JP2022027515A (ja) 溶鋼の脱硫方法および脱硫フラックス
AU2022299766A1 (en) Treatment method of molten steel and steel production method
JP2005179691A (ja) 溶銑の脱珪処理方法
JP2016060964A (ja) 溶銑の脱珪処理方法

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190722

A4 Supplementary search report drawn up and despatched

Effective date: 20191021

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20200608

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602018016293

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C21C0007064000

Ipc: C21C0007000000

RIC1 Information provided on ipc code assigned before grant

Ipc: C21C 7/072 20060101ALI20201009BHEP

Ipc: C21C 7/04 20060101ALI20201009BHEP

Ipc: C21C 7/076 20060101ALI20201009BHEP

Ipc: C21C 7/064 20060101ALI20201009BHEP

Ipc: C21C 7/00 20060101AFI20201009BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20201214

RIN1 Information on inventor provided before grant (corrected)

Inventor name: FUJII, YUSUKE

Inventor name: KIKUCHI, NAOKI

Inventor name: NAKAI, YOSHIE

Inventor name: MASAKI, HIDEYA

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1387105

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210515

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018016293

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1387105

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210428

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210728

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210728

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210830

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210828

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210729

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210428

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018016293

Country of ref document: DE

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

Effective date: 20220131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210828

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602018016293

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20220110

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20220131

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: 20220110

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220802

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220110

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220131

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220131

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220110

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20180110

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20240109

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210428