[go: up one dir, main page]

WO2017018263A1 - Agent de désulfuration, procédé de désulfuration de la fonte en fusion et procédé permettant de produire de la fonte en fusion - Google Patents

Agent de désulfuration, procédé de désulfuration de la fonte en fusion et procédé permettant de produire de la fonte en fusion Download PDF

Info

Publication number
WO2017018263A1
WO2017018263A1 PCT/JP2016/071071 JP2016071071W WO2017018263A1 WO 2017018263 A1 WO2017018263 A1 WO 2017018263A1 JP 2016071071 W JP2016071071 W JP 2016071071W WO 2017018263 A1 WO2017018263 A1 WO 2017018263A1
Authority
WO
WIPO (PCT)
Prior art keywords
desulfurization
hot metal
agent
desulfurizing agent
quicklime
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.)
Ceased
Application number
PCT/JP2016/071071
Other languages
English (en)
Japanese (ja)
Inventor
中井　由枝
菊池　直樹
秀弥 正木
市川　彰
洋晴 井戸
三木　祐司
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=57885668&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2017018263(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
Priority to EP16830368.3A priority Critical patent/EP3327150B1/fr
Priority to KR1020187001100A priority patent/KR102142198B1/ko
Priority to BR112018001331-5A priority patent/BR112018001331B1/pt
Priority to JP2016570900A priority patent/JP6156598B2/ja
Priority to CN201680042971.XA priority patent/CN107849623B/zh
Publication of WO2017018263A1 publication Critical patent/WO2017018263A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • C21C1/00—Refining of pig-iron; Cast iron
    • C21C1/02—Dephosphorising or desulfurising
    • C21C1/025—Agents used for dephosphorising or desulfurising
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0037—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 by injecting powdered material
    • 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
    • C21C7/0645—Agents used for dephosphorising or desulfurising
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D27/00—Stirring devices for molten material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/18—Charging particulate material using a fluid carrier
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/18—Charging particulate material using a fluid carrier
    • F27D2003/185—Conveying particles in a conduct using a fluid

Definitions

  • the present invention relates to a desulfurizing agent, a hot metal desulfurization method, and a hot metal manufacturing method.
  • hot metal discharged from the blast furnace usually contains a high concentration of sulfur (S) that adversely affects the quality of the steel.
  • S sulfur
  • various hot metal pretreatments and molten steel desulfurization are performed according to the required quality.
  • hot metal desulfurization of hot metal also called “hot metal desulfurization”
  • an injection desulfurization method in which desulfurization is performed by blowing a desulfurizing agent into the hot metal, or a desulfurization agent is added to the hot metal stirred by a stirring blade A method such as a mechanical stirring type desulfurization method in which desulfurization is performed by using a known method is known.
  • a desulfurization agent mainly composed of cheap quick lime is used as a refining agent in any of the methods, and the desulfurization reaction proceeds according to the reaction formula shown in the formula (1).
  • a method using a solvent such as fluorite (CaF 2 ) or an alumina-based solvent for the purpose of improving reaction efficiency by promoting hatching of quicklime is known.
  • a solvent such as fluorite (CaF 2 ) or an alumina-based solvent
  • 95 wt% CaO-5 wt% CaF 2 is widely used as a desulfurizing agent mixed with a solvent.
  • these medium solvents are generally expensive, increasing the mixing ratio of the medium solvent in the desulfurizing agent causes an increase in the cost of the desulfurizing agent.
  • the CaO concentration in the desulfurizing agent is lowered, there is a concern that the reaction efficiency of the desulfurizing agent is lowered.
  • calcium carbide-based and soda-based desulfurization agents have been put into practical use, both of which have advantages and disadvantages.
  • Calcium carbide-based desulfurization agents have a strong desulfurization ability, but have problems such as the generation of acetylene gas in the post-treatment of slag produced by the desulfurization treatment.
  • calcium carbide-based desulfurization agents are also dangerous and difficult to handle.
  • soda-based desulfurization agents are relatively inexpensive, they are highly alkaline and thus have a great influence on refractories such as furnaces and containers. In addition, since the soda-based desulfurization agent contains Na in the exhaust gas, it needs to be removed.
  • a soda-based desulfurization agent has a high Na 2 O content in the slag, there are restrictions on its reuse in cement and the like. For this reason, it cannot be said that it is a desirable desulfurization agent like fluorine from the influence on the environment.
  • a method using metal Mg as a desulfurization agent is also well known. Metal Mg easily reacts with S in the hot metal to produce MgS.
  • the boiling point is as low as 1100 ° C., there is a risk that the hot metal vaporizes vigorously in the hot metal at 1250 ° C. to 1500 ° C. and the hot metal is scattered.
  • the generated Mg vapor is not sufficiently contributed to the desulfurization reaction and is diffused into the atmosphere, so that the efficiency is poor. Furthermore, since metal Mg is very expensive, it causes an increase in cost for the desulfurization treatment.
  • Patent Documents 2 and 3 disclose methods for controlling density, specific surface area, pore diameter capacity, and the like as lime properties in hot metal desulfurization by injection desulfurization. According to Patent Documents 2 and 3, by controlling these lime properties, the rising speed of the desulfurizing agent blown into the hot metal can be controlled (lowered), and the reaction between the hot metal and the desulfurizing agent is promoted. be able to.
  • Patent Documents 2 and 3 are directed to the injection desulfurization method as the hot metal desulfurization method, and are not the optimal lime property in the mechanical stirring desulfurization method.
  • the particle size of the target desulfurization agent is as small as 200 ⁇ m or less.
  • a desulfurizing agent having a large particle size is used from the viewpoint of securing the addition yield.
  • a method for securing the reaction interface area using such a desulfurizing agent having a large particle size is no mention of a method for securing the reaction interface area using such a desulfurizing agent having a large particle size.
  • a powdery desulfurizing agent added to the hot metal bath surface is usually entrained in the hot metal, and the desulfurizing agent reacts with S in the hot metal.
  • the desulfurization efficiency is lowered because the reaction interfacial area is reduced by agglomeration of the desulfurizing agent.
  • the slag after the desulfurization treatment becomes agglomerated particles of several mm to several tens mm.
  • a method for improving the reaction efficiency in the mechanical stirring type desulfurization method a method of projecting a powdered desulfurization agent onto the bath surface (also referred to as a projection method) is known. Since the projection method suppresses the aggregation of the desulfurizing agent when being entrained in the hot metal as compared with the upper addition method, the substantial reaction interface area is increased and the desulfurization ability can be improved. However, even in such a projection method, aggregation of the projected desulfurizing agent still proceeds, so that the reaction interface area of the desulfurizing agent itself could not be fully utilized.
  • Patent Documents 4 and 5 disclose a method of projecting a desulfurizing agent using a carrier gas.
  • the desulfurization agent itself can be prevented from agglomerating by promoting the penetration of the desulfurization agent into the hot metal.
  • no consideration is given to the properties of quicklime, so a technique for further improving the desulfurization efficiency of quicklime is required from the viewpoint of the lime properties.
  • JP-A-8-268717 Japanese Patent No. 5101988 JP 62-56509 A Japanese Patent No. 5045031 Japanese Patent No. 5195737
  • the present invention has been made paying attention to the above-mentioned problems, and aims to provide a desulfurization agent, a hot metal desulfurization method, and a hot metal manufacturing method that are excellent in desulfurization efficiency and can reduce the cost of desulfurization treatment. Yes.
  • a desulfurization agent used for hot metal desulfurization and the total pore volume, which is the sum of the volume of pores having a pore diameter of 0.5 ⁇ m or more and 10 ⁇ m or less, is 0.1 mL / g or more.
  • a desulfurizing agent characterized in that it comprises according to one aspect of the present invention, when the hot metal is desulfurized with a mechanically stirring desulfurization apparatus, the total pore volume, which is the sum of the pore volumes having a pore diameter of 0.5 ⁇ m or more and 10 ⁇ m or less, is 0.00.
  • a hot metal desulfurization method characterized by using a desulfurization agent containing powdered quicklime with an average particle size of 210 ⁇ m to 500 ⁇ m. According to one aspect of the present invention, there is provided a hot metal production method using the hot metal desulfurization method.
  • a desulfurization agent for reducing the cost of desulfurization treatment.
  • FIG. 1 shows the mechanical stirring type desulfurization apparatus 1 used in the first test
  • Table 1 shows the conditions of the apparatus and test method in which the first test was performed.
  • the mechanical stirring type desulfurization apparatus 1 is a refining apparatus for desulfurizing a hot metal 3 accommodated in a hot metal ladle 2.
  • the hot metal ladle 2 is placed at the processing position while being placed on the carriage 4.
  • the ladle diameter of the hot metal ladle 2 is 4 m
  • the weight of the hot metal 3 is 300 t / ch
  • the temperature of the hot metal 3 is 1280 ° C. or higher and 1330 ° C. or lower
  • the S concentration ([[ S]) was set to 0.025 wt% or more and 0.035 wt% or less.
  • ch charge is a unit indicating the number of desulfurization processes performed for each hot metal ladle 2 by the mechanical stirring desulfurization apparatus 1, and 300 t / ch is the weight of the hot metal 3 processed in one desulfurization process ( The weight of the hot metal 3 accommodated in the hot metal ladle 2 is 300 t.
  • the mechanical stirring desulfurization apparatus 1 includes a stirring blade (impeller) 5, a projection unit 6, and an upper addition unit 7.
  • the stirring blade 5 is a refractory stirrer, and is connected to a shaft at the upper end in the vertical direction (vertical direction with respect to the plane of FIG. 1), and protrudes in a direction perpendicular to the central axis centering on this shaft. With wings.
  • the upper end side of the shaft of the stirring blade 5 is connected to a rotating device and a lifting device (not shown).
  • the stirring blade 5 rotates around the shaft when the shaft receives rotational driving from the rotating device.
  • the stirring blade 5 is configured to be vertically movable by the lifting operation of the lifting device.
  • the projection unit 6 includes a hopper 8, a rotary feeder 9, and a lance 10.
  • the hopper 8 contains a desulfurizing agent.
  • the rotary feeder 9 cuts out the desulfurizing agent accommodated in the hopper 8 at a predetermined cutting speed and supplies it to the lance 10.
  • the lance 10 is a lance of 65A, and is arranged above the bath surface of the hot metal 3 so as to extend in the vertical direction.
  • the lance 10 sprays the desulfurizing agent on the bath surface of the hot metal 3 by injecting the desulfurizing agent cut out from the rotary feeder 9 together with nitrogen which is a carrier gas supplied from a carrier gas supply device (not shown).
  • the upper addition means 7 includes a hopper 11, a rotary feeder 12, and a charging chute 13.
  • the hopper 11 contains a desulfurizing agent.
  • the rotary feeder 12 cuts out the desulfurizing agent accommodated in the hopper 11 at a predetermined cutting speed and supplies it to the charging chute 13.
  • the lower end of the charging chute 13 is arranged above the bath surface of the hot metal 3, and the desulfurizing agent supplied from the rotary feeder 12 is dropped freely from the tip to be poured into the bath surface of the hot metal 3.
  • the desulfurizing agent was added to the hot metal 3 by any one of the addition method using the projection means 6 or the upper addition method using the upper addition means 7 to perform the desulfurization treatment.
  • the flow rate of nitrogen gas was set to 0 Nm 3 / min to 7 Nm 3 / min, and the desulfurizing agent was added at an addition rate of 200 kg / min.
  • the desulfurization agent was added at an addition rate of 1000 kg / min.
  • the desulfurization agent is only powdered quicklime, and desulfurization treatment is performed without adding additives other than components inevitably contained in the quicklime, and 5 kg is applied by the projection method or the upper addition method. / T (addition amount per ton of hot metal) was added. Furthermore, in order to investigate the relationship between the total pore volume of quicklime and the desulfurization rate (the ratio of the amount of change in the S concentration before and after the treatment with respect to the S concentration before the treatment) and the relationship between the particle size of the quicklime and the desulfurization rate, The desulfurization treatment was performed under the conditions in which the total pore volume of quicklime or the particle size of quicklime was changed.
  • the total pore volume of quicklime is calculated from the measured pore size distribution.
  • the method for measuring the pore size distribution is as follows. First, quick lime was dried at 120 ° C. for 4 hours as a pretreatment. Next, using an Autopore IV9520 manufactured by Micromerites, the pore distribution of the dried quicklime having a pore diameter of about 0.0036 ⁇ m to 200 ⁇ m was obtained by mercury porosimetry, and a cumulative pore volume curve was calculated. Further, the total pore volume of pores having a diameter of 0.5 ⁇ m to 10 ⁇ m was determined from the calculated cumulative pore volume curve. The pore diameter was calculated using the Washburn equation (equation (2)).
  • the particle diameter is an average particle diameter, and a predetermined average particle diameter is obtained by sieving the desulfurizing agent.
  • the method for measuring the average particle size of the desulfurizing agent is as follows. First, 500 g of a desulfurizing agent is collected at the time of shipment from the manufacturer or when the hopper 8 is loaded. Subsequently, the collected desulfurizing agent was sieved into 9 stages of 45 ⁇ m or less, 45 ⁇ m to 75 ⁇ m, 75 ⁇ m to 100 ⁇ m, 100 ⁇ m to 125 ⁇ m, 125 ⁇ m to 150 ⁇ m, 150 ⁇ m to 300 ⁇ m, 300 ⁇ m to 500 ⁇ m, 500 ⁇ m to 1000 ⁇ m, 1000 ⁇ m or more.
  • the average particle diameter was calculated by calculating the weight ratio of the formula (3) for the sieved desulfurizing agent.
  • D a is an average particle diameter (mm)
  • d i is an average particle diameter (medium value of sieve mesh) (mm) in each particle diameter range
  • w i is a desulfurizing agent on each sieve. The weight (kg) is shown.
  • the relationship between the total pore volume, which is the sum of the volumes of pores having a pore diameter of 0.5 ⁇ m or more and 10 ⁇ m or less, and the desulfurization rate when the projection method or the top addition method is used is shown. It is shown in 2.
  • the particle size of the desulfurization agent was 1 mm or less.
  • the desulfurization rate is remarkably increased when the total pore volume having a pore diameter of 0.5 ⁇ m or more and 10 ⁇ m or less is 0.1 mL / g or more. It was confirmed that a high desulfurization rate of 80% or more was obtained.
  • the cost for improving the desulfurization rate was increased by using the projection method as compared with the upper addition method.
  • FIG. 3 shows the relationship between the average particle size of the desulfurizing agent and the desulfurization rate when the projection method or the top addition method is used.
  • the total pore volume having a pore diameter of 0.5 ⁇ m or more and 10 ⁇ m or less was 0.2 mL / g.
  • the desulfurization rate was remarkably increased when the average particle size of the desulfurizing agent was in the range of 210 ⁇ m or more and 500 ⁇ m or less.
  • the desulfurization rate was further increased when the average particle size of the desulfurizing agent was 230 ⁇ m or more.
  • the cost for improving the desulfurization rate was increased by using the projection method as compared with the upper addition method.
  • At least one of the top addition method and the projection method is generally used as a desulfurization agent addition method in the mechanical stirring desulfurization method.
  • a desulfurization agent addition method in the mechanical stirring desulfurization method, unlike the injection desulfurization method in which the added desulfurizing agent completely enters the hot metal, it is difficult to add the small-diameter desulfurization agent into the hot metal with a high yield.
  • the particle size of the desulfurizing agent to be added is important for improving the yield.
  • a desulfurization agent with a small particle size is used, and if this desulfurization agent can penetrate into the hot metal, it is possible to secure a reaction interface area with the hot metal, thus improving the desulfurization reaction efficiency.
  • the desulfurization agent having a small particle diameter becomes difficult to penetrate into the hot metal as the particle diameter becomes small, there is a high possibility that it will not contribute to the reaction even if it is added.
  • the particle size of the desulfurizing agent to be added is increased, it is advantageous for penetration into the hot metal and the yield is improved, but the reaction interfacial area is reduced, which is disadvantageous from the viewpoint of desulfurization reaction. For this reason, in order to promote the reaction while ensuring the yield to the hot metal, it is important to ensure both an appropriate particle size of the desulfurizing agent and increase the reaction efficiency.
  • the inventors have determined that the pore diameter is 0.5 ⁇ m or more and 10 ⁇ m or less in order to improve the desulfurization efficiency in the mechanical stirring desulfurization method using quick lime as a desulfurizing agent. It was found that the presence of pores is important, and it is important to use a desulfurization agent having a total pore volume of 0.1 mL / g or more. Furthermore, it has been found that by using a desulfurizing agent having an average particle size of 210 ⁇ m or more and 500 ⁇ m or less, an appropriate particle size for improving the yield when added to molten iron can be secured. Thus, desulfurization efficiency can be further improved by controlling the average particle diameter in addition to the pores.
  • the present inventors performed desulfurization treatment under various stirring conditions as a second test in order to investigate the influence of the stirring conditions on the desulfurization rate in the projection method.
  • the desulfurizing agent is only powdery quick lime as in the first test, the total pore volume having a pore diameter of 0.5 ⁇ m or more and 10 ⁇ m or less is 0.1 mL / g or more, and the particle diameter is 2 mm.
  • the following quicklime was used.
  • the addition amount of the desulfurization agent was a fixed amount of 5 kg / t, and the desulfurization treatment was performed without adding the additive other than being inevitably contained in the lime.
  • the desulfurization treatment was performed using the mechanical stirring desulfurization apparatus 1 shown in FIG.
  • the 2nd test when adding a desulfurization agent, only the projection means 6 was used, and the addition conditions of the desulfurization agent were made the same as the 1st test.
  • the influence of these stirring conditions on the desulfurization rate was investigated by changing the bath surface position of the hot metal 3 to which the desulfurizing agent was sprayed and the rotation speed of the stirring blade 5.
  • the desulfurization rate was different depending on the number of rotations of the stirring blade 5 and the spraying position of the desulfurizing agent, but these were the flow rates in the horizontal direction of the bath surface of the hot metal 3 at the position where the desulfurizing agent was sprayed. I was able to organize it.
  • the horizontal flow velocity is the flow velocity in the horizontal tangential direction of the swirling flow generated by mechanical stirring at the position where the desulfurizing agent is sprayed onto the bath surface of the molten iron 3.
  • FIG. 4 shows the relationship between the horizontal flow velocity of the bath surface and the desulfurization rate. As shown in FIG.
  • the hot metal 3 is desulfurized using the mechanical stirring desulfurization apparatus 1 shown in FIG.
  • the mechanical agitation desulfurization apparatus 1 includes a lid (not shown) that covers the upper opening of the hot metal ladle 2 and an exhaust duct (not shown) that is provided on the lid and is connected to an exhaust device (not shown). Gases and dust generated during the desulfurization process are discharged to the exhaust device through the exhaust duct.
  • the hot metal ladle 2 in which the hot metal 3 is accommodated is placed on the cart 4, and the cart 4 moves until the stirring blade 5 reaches a predetermined position with respect to the hot metal pan 2.
  • the stirring blade 5 is lowered by the lifting device, so that the stirring blade 5 is immersed in the hot metal 3.
  • the stirring blade 5 is rotated by a rotating device, and the rotation speed is increased until a predetermined rotation speed is reached.
  • generated gas and dust are discharged from the exhaust duct by the exhaust device.
  • the desulfurizing agent is added to the hot metal 3 by the projection means 6 or the upper addition means 7.
  • the desulfurization agent is quick lime having a total pore volume of 0.1 mL / g or more and an average particle size of 210 ⁇ m or more and 500 ⁇ m or less, which is the sum of the pores having a pore diameter of 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the minimum value of the particle size of quicklime is preferably 40 ⁇ m or more in consideration of scattering at the time of addition.
  • the quicklime may be calcined in any furnace such as a kiln furnace, a Merz furnace, or a Beckenbach furnace.
  • the desulfurizing agent cut out by the rotary feeder 9 is added to the hot metal 3 by being blown into the bath surface of the hot metal 3 from the lance 10 together with a carrier gas such as nitrogen. At this time, it is preferable that the desulfurizing agent is blown into a position where the horizontal flow velocity on the bath surface of the molten iron 3 is 1.1 m / s or more and 11.9 m / s or less. The position where the flow velocity on the bath surface falls within the above range is calculated in advance from the stirring conditions such as the rotational speed of the stirring blade 5 and the spraying position of the desulfurizing agent.
  • the desulfurizing agent cut out by the rotary feeder 9 is added to the bath surface of the hot metal 3 through the charging chute 13.
  • the hot metal 3 is stirred by the stirring blade 5 until a predetermined time elapses. Thereafter, the rotation speed decreases until the rotation of the stirring blade 5 is stopped by the rotating device, and after the rotation is stopped, the stirring blade 5 is raised by the lifting device. Next, the slag generated by the desulfurization process floats, covers the bath surface of the molten iron 3, and becomes stationary, thereby completing the desulfurization process. Thereby, the hot metal 3 having a desired S concentration is manufactured.
  • the desulfurizing agent may be a mixture of quick lime whose total pore volume and particle size are within the above ranges and quick lime whose total pore volume and particle size are outside the above ranges.
  • the desulfurizing agent may be added with a solvent medium such as alumina in addition to quick lime whose total pore volume and particle size are within the above ranges.
  • the desulfurization agent which concerns on this invention does not contain the solvent which has at least 1 eluting element among fluorine, sodium, and potassium.
  • the desulfurization agent is used as the refining agent when performing the desulfurization treatment, but the present invention is not limited to this example.
  • a refining agent that further accelerates the desulfurization reaction an aluminum dross powder containing metal Al or a deoxidizer such as metal Al may be added.
  • the deoxidizing agent may be stored in a hopper different from the desulfurizing agent, and may be added to the hot metal 3 through the charging chute 13 after being cut out from the hopper.
  • a medium solvent such as fluorite or soda ash may be added as a refining agent.
  • the medium solvent may be added in a state of being mixed with the desulfurizing agent in advance, or after being stored in a hopper different from the desulfurizing agent and cut out from the hopper, the hot metal 3 is supplied via the charging chute 13. May be added.
  • the projection means 6 was set as the structure provided with one lance 10, this invention is not limited to this example.
  • two or more lances 10 may be provided.
  • the desulfurization agent was set as the structure used for the mechanical stirring type hot metal desulfurization method, this invention is not limited to this example.
  • quick lime having a total pore volume of 0.1 mL / g or more which is the sum of the volume of pores having a pore diameter of 0.5 ⁇ m or more and 10 ⁇ m or less, is used as the desulfurization agent, as shown in FIG.
  • the desulfurization rate increases remarkably as the interfacial area increases.
  • the desulfurizing agent according to the present invention may be used in a desulfurization treatment method other than the mechanical stirring type hot metal desulfurization method.
  • the desulfurizing agent according to one aspect of the present invention is a desulfurizing agent used for hot metal desulfurization, and has a total pore volume of 0, which is the sum of the pore volumes with a pore diameter of 0.5 ⁇ m to 10 ⁇ m. Contains 1 mL / g or more of quicklime.
  • the desulfurization efficiency by quick lime can be improved by setting the total pore volume of quick lime in the above range. This makes it possible to improve production efficiency by shortening the desulfurization time, reduce temperature loss and process costs, and reduce the amount of dust and slag generated with the desulfurization process.
  • the cost for the refining agent can be reduced and handling is easy as compared with a desulfurization agent other than a CaO-based one having high reaction efficiency.
  • the present invention can be applied to both the addition method and the projection method in the mechanical stirring type desulfurization method.
  • quick lime is in the form of a powder having an average particle size of 210 ⁇ m or more and 500 ⁇ m or less, and is used in a mechanical stirring type hot metal desulfurization method.
  • the desulfurization efficiency by quicklime can be improved more by making the average particle diameter of quicklime into the said range.
  • the desulfurization efficiency improvement effect by the quick lime of the said structure can be acquired more effectively by using a desulfurization agent for the mechanical stirring type hot metal desulfurization method.
  • quick lime has an average particle size of 230 ⁇ m or more and 500 ⁇ m or less.
  • the desulfurization efficiency can be further improved as compared with the configuration of (2) above.
  • at least any one of fluorine, potassium and sodium is not substantially contained.
  • the state in which at least one element of fluorine, potassium, and sodium is substantially not included means that at least one element is included by intentional addition, except for inevitable traces of contamination. That is not.
  • the amount of expensive medium solvent used is reduced, and the cost required for the refining agent in the desulfurization treatment can be reduced.
  • the slag after the desulfurization treatment can be used effectively.
  • it does not contain sodium it is not necessary to remove Na from the exhaust gas, and the refractory cost can be reduced.
  • the cost for the refining agent can be reduced, and handling becomes easy.
  • the desulfurizing agent may include components inevitably contained in quicklime.
  • the medium solvent which has eluting elements such as sodium and potassium
  • the usage-amount of an expensive medium solvent can be reduced and the cost concerning the refining agent in a desulfurization process can be reduced.
  • the slag after the desulfurization treatment can be used effectively.
  • it does not contain sodium it is not necessary to remove Na from the exhaust gas, and the refractory cost can be reduced.
  • the hot metal desulfurization method is the sum of the pore volumes at which the pore diameter becomes 0.5 ⁇ m or more and 10 ⁇ m or less when the hot metal 3 is desulfurized by the mechanical stirring desulfurization apparatus 1.
  • a desulfurization agent containing powdered quicklime having a total pore volume of 0.1 mL / g or more and an average particle diameter of 210 ⁇ m or more and 500 ⁇ m or less is used.
  • quick lime has an average particle size of 230 ⁇ m or more and 500 ⁇ m or less. According to the configuration of the above (7), the same effect as the configuration of the above (3) can be obtained.
  • the mechanical stirring type desulfurization apparatus 1 includes a stirring blade 5 for stirring the hot metal 3 and a desulfurizing agent on the bath surface of the hot metal 3 from above the hot metal 3 together with a carrier gas.
  • the hot metal 3 is desulfurized, the hot metal is stirred using the stirring blade 5 and the hot metal 3 is stirred to desulfurize the bath surface using the upper blow lance 10. Spray the agent.
  • the improvement effect of the desulfurization efficiency of quicklime can be enlarged more compared with the case where a desulfurization agent is added using the upper addition method.
  • Example 1 the hot metal 3 was desulfurized using the hot metal desulfurization method according to the above embodiment, using the mechanical stirring desulfurization apparatus 1 shown in FIG.
  • the hot metal 3 subjected to the desulfurization treatment was obtained by performing two-stage desiliconization treatment in the hot metal ladle, which is a blast furnace casting floor and a receiving vessel, after leaving the blast furnace.
  • Example 1 desulfurization treatment was performed under a plurality of conditions using a desulfurizing agent in which the total pore volume, particle size, and ratio of quicklime were changed within the range of the above embodiment. Furthermore, in Example 1, the addition amount of the desulfurization agent is a constant amount of 5 kg / t, and when adding the desulfurization agent, either the projection method by the projection means 6 or the upper addition method by the upper addition means 7 is used. The desulfurization treatment was carried out under a plurality of conditions using. The desulfurization agent addition conditions and stirring conditions were the same as in the first test shown in Table 1. In any addition method of the desulfurizing agent, the position of the bath surface to which the desulfurizing agent is added is the same position. And desulfurization efficiency was evaluated by calculating a desulfurization rate from the S concentration of the hot metal 3 measured before and after the desulfurization treatment.
  • Example 1 as a comparative example, the desulfurization treatment was performed under the conditions using the injection desulfurization method, the total pore volume of quick lime, and the average particle diameter being different from the range of the above embodiment.
  • the desulfurization efficiency was evaluated.
  • Table 2 shows the test level and desulfurization efficiency evaluation results in Example 1.
  • the ratio (%) of quicklime indicates the ratio of quicklime that has a pore diameter of 0.5 ⁇ m or more and 10 ⁇ m or less and a particle diameter of 2 mm or less among the quicklime that is a desulfurization agent.
  • 0.5-10 ⁇ m pore total volume (mL / g) represents the total pore volume, which is the sum of the volumes of pores having a pore diameter of 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the average pore diameter of the quicklime used was 0.1 ⁇ m to 0.3 ⁇ m.
  • Example 2 when the addition method of the desulfurizing agent was the projection method, the influence of the stirring conditions on the desulfurization efficiency was investigated.
  • a desulfurization agent was added using the projection method in the same manner as in Examples 1-1 to 1-15, and the sum of the total pore volumes, the particle diameters, and the stirring conditions of quick lime as a desulfurization agent were changed.
  • the desulfurization treatment was performed under the conditions of: Table 3 shows the test level and the evaluation result of the desulfurization efficiency in Example 2.
  • the difference in the stirring conditions which is the difference in the number of revolutions of the stirring blade 5 and the spraying position of the desulfurizing agent, was arranged by the horizontal flow velocity on the bath surface of the hot metal 3 calculated from each condition.
  • the horizontal flow velocity on the bath surface of the hot metal 3 at the position where the desulfurizing agent is sprayed is in the range of 1.1 m / s to 11.5 m / s. Under the conditions of 9, 2-15 to 2-19, it was confirmed that the desulfurization rate was 97% or higher, which was higher than other conditions.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)

Abstract

La présente invention porte sur un procédé de désulfuration de la fonte en fusion, qui présente une excellente efficacité de désulfuration et peut réduire le coût nécessaire pour le traitement de désulfuration ; et sur un procédé permettant de produire de la fonte en fusion. Un agent de désulfuration qui est utilisé pour la désulfuration de la fonte en fusion et contient de la chaux vive qui présente un volume total de pores égal ou supérieur à 0,1 ml/g, ledit volume total de pores étant la somme des volumes de pores présentant un diamètre de pore compris entre 0,5 μm et 10 μm (inclus).
PCT/JP2016/071071 2015-07-24 2016-07-15 Agent de désulfuration, procédé de désulfuration de la fonte en fusion et procédé permettant de produire de la fonte en fusion Ceased WO2017018263A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP16830368.3A EP3327150B1 (fr) 2015-07-24 2016-07-15 Agent de désulfuration, procédé de désulfuration de la fonte en fusion et procédé permettant de produire de la fonte en fusion
KR1020187001100A KR102142198B1 (ko) 2015-07-24 2016-07-15 탈황제, 용선 탈황 방법 및 용선의 제조 방법
BR112018001331-5A BR112018001331B1 (pt) 2015-07-24 2016-07-15 Fluxo de dessulfurização, método para dessulfurizar metal quente e método para produzir metal quente
JP2016570900A JP6156598B2 (ja) 2015-07-24 2016-07-15 脱硫剤、溶銑脱硫方法および溶銑の製造方法
CN201680042971.XA CN107849623B (zh) 2015-07-24 2016-07-15 脱硫剂、铁水脱硫方法和铁水的制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015146930 2015-07-24
JP2015-146930 2015-07-24

Publications (1)

Publication Number Publication Date
WO2017018263A1 true WO2017018263A1 (fr) 2017-02-02

Family

ID=57885668

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/071071 Ceased WO2017018263A1 (fr) 2015-07-24 2016-07-15 Agent de désulfuration, procédé de désulfuration de la fonte en fusion et procédé permettant de produire de la fonte en fusion

Country Status (7)

Country Link
EP (1) EP3327150B1 (fr)
JP (1) JP6156598B2 (fr)
KR (1) KR102142198B1 (fr)
CN (1) CN107849623B (fr)
BR (1) BR112018001331B1 (fr)
TW (1) TWI616402B (fr)
WO (1) WO2017018263A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018135344A1 (fr) * 2017-01-19 2018-07-26 Ｊｆｅスチール株式会社 Procédé de traitement de désulfuration destiné à de l'acier fondu, et agent de désulfuration

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6256509A (ja) * 1985-09-04 1987-03-12 Kawasaki Steel Corp 生石灰を用いる溶銑脱硫方法
JPS62283847A (ja) * 1986-05-29 1987-12-09 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
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

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS511988B1 (fr) 1968-04-20 1976-01-22
JPS5045031Y2 (fr) 1971-10-29 1975-12-20
JPS59157209A (ja) * 1983-02-25 1984-09-06 Sumitomo Metal Ind Ltd 溶鉄の予備処理方法
JPH08268717A (ja) 1995-03-30 1996-10-15 Ishikawajima Harima Heavy Ind Co Ltd 脱硫用石灰石の前処理方法
CN1368537A (zh) * 2001-02-09 2002-09-11 王铁钢 燃气高效脱硫剂
CN1249208C (zh) * 2002-10-11 2006-04-05 天津钢管还原铁厂 海绵铁高效脱硫剂
JP4961787B2 (ja) * 2006-03-20 2012-06-27 Ｊｆｅスチール株式会社 溶銑の脱硫方法
JP5130663B2 (ja) * 2006-06-09 2013-01-30 Ｊｆｅスチール株式会社 溶融鉄の精錬方法
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
JP5195737B2 (ja) 2009-12-24 2013-05-15 Ｊｆｅスチール株式会社 溶銑の脱硫方法
JP5177170B2 (ja) * 2010-05-07 2013-04-03 Ｊｆｅスチール株式会社 溶銑の脱硫方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6256509A (ja) * 1985-09-04 1987-03-12 Kawasaki Steel Corp 生石灰を用いる溶銑脱硫方法
JPS62283847A (ja) * 1986-05-29 1987-12-09 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
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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018135344A1 (fr) * 2017-01-19 2018-07-26 Ｊｆｅスチール株式会社 Procédé de traitement de désulfuration destiné à de l'acier fondu, et agent de désulfuration
KR20190108136A (ko) * 2017-01-19 2019-09-23 제이에프이 스틸 가부시키가이샤 용강의 탈황 처리 방법 및 탈황제
EP3572534B1 (fr) * 2017-01-19 2021-04-28 JFE Steel Corporation Procede de traitement de désulfuration d'acier fondu et agent de désulfuration
KR102290861B1 (ko) 2017-01-19 2021-08-17 제이에프이 스틸 가부시키가이샤 용강의 탈황 처리 방법 및 탈황제

Also Published As

Publication number Publication date
JPWO2017018263A1 (ja) 2017-07-27
EP3327150A1 (fr) 2018-05-30
BR112018001331B1 (pt) 2021-09-28
KR20180016593A (ko) 2018-02-14
CN107849623A (zh) 2018-03-27
KR102142198B1 (ko) 2020-08-06
BR112018001331A2 (pt) 2018-09-11
EP3327150B1 (fr) 2019-12-25
JP6156598B2 (ja) 2017-07-05
EP3327150A4 (fr) 2018-05-30
TW201714828A (zh) 2017-05-01
TWI616402B (zh) 2018-03-01
CN107849623B (zh) 2019-06-18

Similar Documents

Publication Publication Date Title
CN102471814B (zh) 铁水的脱硫方法
JP4845078B2 (ja) 溶銑の脱硫方法
JP5691207B2 (ja) 溶銑の脱硫処理用精錬容器及び脱硫処理方法
JP5195737B2 (ja) 溶銑の脱硫方法
JP5177170B2 (ja) 溶銑の脱硫方法
JP6156598B2 (ja) 脱硫剤、溶銑脱硫方法および溶銑の製造方法
JP4998676B2 (ja) インペラーを用いた溶融金属の攪拌方法
JP5045031B2 (ja) 溶銑の脱硫剤及び脱硫処理方法
JP4453532B2 (ja) 溶銑の脱硫方法
JP6369516B2 (ja) 機械攪拌式溶銑脱硫方法
JP6402762B2 (ja) 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
JP4635672B2 (ja) 溶融金属の精錬方法
JP5066923B2 (ja) 溶銑の脱硫処理方法
JP5130663B2 (ja) 溶融鉄の精錬方法
JP4984928B2 (ja) 溶銑の脱硫方法
JP5446300B2 (ja) 溶銑の脱硫処理方法
JP2010116612A (ja) 溶銑の脱硫方法
JP2018172719A (ja) 溶銑の脱硫方法
JP6238019B2 (ja) 復硫の少ない溶銑脱硫方法
WO2016142970A1 (fr) Procédé de désulfuration de fer en fusion et dispositif de désulfuration de fer en fusion
JP2006336036A (ja) 溶銑の脱硫処理方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2016570900

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16830368

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20187001100

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2016830368

Country of ref document: EP

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112018001331

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112018001331

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20180122