WO2011002094A1 - Method of desulfurization of molten iron - Google Patents
Method of desulfurization of molten iron Download PDFInfo
- Publication number
- WO2011002094A1 WO2011002094A1 PCT/JP2010/061366 JP2010061366W WO2011002094A1 WO 2011002094 A1 WO2011002094 A1 WO 2011002094A1 JP 2010061366 W JP2010061366 W JP 2010061366W WO 2011002094 A1 WO2011002094 A1 WO 2011002094A1
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- WIPO (PCT)
- Prior art keywords
- desulfurization
- hot metal
- stirring blade
- slag
- agent
- Prior art date
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 166
- 230000023556 desulfurization Effects 0.000 title claims abstract description 166
- 238000000034 method Methods 0.000 title claims abstract description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title abstract description 12
- 229910052742 iron Inorganic materials 0.000 title abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 123
- 239000002245 particle Substances 0.000 claims abstract description 43
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims description 130
- 239000002184 metal Substances 0.000 claims description 130
- 239000002893 slag Substances 0.000 claims description 77
- 238000003756 stirring Methods 0.000 claims description 69
- 238000007664 blowing Methods 0.000 claims description 52
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 44
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 44
- 239000004571 lime Substances 0.000 claims description 44
- 238000012545 processing Methods 0.000 claims description 20
- 239000012159 carrier gas Substances 0.000 abstract description 15
- 230000002776 aggregation Effects 0.000 abstract description 12
- 238000004220 aggregation Methods 0.000 abstract description 11
- 238000005422 blasting Methods 0.000 abstract description 2
- 230000003009 desulfurizing effect Effects 0.000 description 76
- 238000006243 chemical reaction Methods 0.000 description 31
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 20
- 239000007789 gas Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 13
- 238000009434 installation Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 239000000428 dust Substances 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000005901 DNA-dependent transcriptional open complex formation Effects 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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- 238000001764 infiltration Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
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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
-
- 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
Definitions
- the present invention uses a mechanical stirring desulfurization apparatus equipped with a stirring blade, and a desulfurization agent via a top lance on the hot metal bath surface stirred by the stirring blade. ) Is sprayed and added to the hot metal (molten iron) for desulfurization.
- the hot metal desulfurization treatment is generally performed using a solid desulfurization agent such as lime (CaO).
- a lime-based desulfurization agent CaO-based desulfurization agent
- a hot metal transfer container such as a toppedo car or hot-metal ladle using a blowing injection lance.
- the injection desulfurization method to be added or a stirring blade (also referred to as “impeller”) is immersed in the hot metal in the hot metal conveying container, and the lime-based desulfurizing agent is added on top while stirring the hot metal with the rotating stirring blade (top addition / addition)
- a mechanical stirring desulfurization method has been performed.
- the particle size of the desulfurization agent to be added size in diameter
- the desulfurization reaction efficiency will be improved.
- the desulfurization agent is cut out (add) from the hopper, and the desulfurization agent is added to the treatment vessel from the inlet installed above the treatment vessel such as a hot metal ladle. Is common.
- Patent Document 1 discloses that in a hot metal desulfurization method using a mechanical stirring type desulfurization apparatus, a desulfurizing agent is placed on the bath surface of the hot metal being stirred by a stirring blade via an upper blowing lance.
- a method of performing a desulfurization process by blasting with a carrier gas has been proposed.
- Patent Document 1 since a fine-sized desulfurization agent having excellent reactivity is added together with a carrier gas, scattering during addition is reduced, and the addition yield of the desulfurization agent is improved.
- the fine-grain desulfurization agent has a large reaction interface area, and therefore, the desulfurization reaction is promoted, and the desulfurization rate can be remarkably improved.
- Patent Document 1 An upper blowing lance is used to avoid aggregation of the desulfurizing agent, which is a problem when the desulfurizing agent is added from above the processing vessel, and to increase a substantial reaction interface area.
- the powdery desulfurizing agent is sprayed on the hot metal bath surface together with the carrier gas.
- aggregation is a phenomenon in which the added powdery desulfurizing agent coalesces in the hot metal or on the hot metal after addition and grows into a spherical shape. In order to substantially increase the reaction interface area, the aggregation is suppressed. There is a need to.
- Patent Document 1 does not define the particle size of the desulfurizing agent, and therefore, desulfurization in which the desulfurizing agent is added at a high addition yield and aggregation of the added desulfurizing agent is prevented. It is difficult to obtain a stable treatment.
- the hot metal may be subjected to desiliconization treatment and dephosphorization treatment before desulfurization treatment of the hot metal.
- the desulfurization treatment is performed after removing the slag generated in the desiliconization process or the dephosphorization process in the previous process, but the slag in the previous process cannot be completely removed, and the slag in the previous process is unavoidable. Mixing and the amount of mixing vary. Since both the desiliconization process and the dephosphorization process are refining utilizing an oxidation reaction, the mixed slag has a high degree of oxidation.
- This mixed slag is caught in the hot metal when the hot metal is stirred by the stirring blade, and is reduced by the carbon in the hot metal. Since this phenomenon is equivalent to the addition of oxygen to hot metal, it works against the desulfurization reaction, which is reductive refining. That is, the desulfurization reaction is inhibited by the mixed slag. This phenomenon has a greater effect when sprayed with a top blowing lance than when the desulfurizing agent is added on top. In the top addition method, mixed slag and desulfurizing agent (upper added flux) aggregate on the bath surface, and the mixed slag is not directly involved in the hot metal and the desulfurization reaction is difficult to be inhibited by the mixed slag. Then, there are few desulfurization agents (upper addition flux) which exist on a hot metal surface, and it is because the mixed slag is often caught as it is.
- the present invention has been made in view of the above circumstances, and its object is to use a mechanical stirring type desulfurization apparatus equipped with a stirring blade, and a hot metal bath surface being stirred by the stirring blade via an upper blowing lance.
- a mechanical stirring type desulfurization apparatus equipped with a stirring blade, and a hot metal bath surface being stirred by the stirring blade via an upper blowing lance.
- desulfurization treatment of hot metal by spraying and adding desulfurizing agent it is possible to add desulfurizing agent with a high addition yield, and at the same time, it prevents aggregation of the added desulfurizing agent, which makes it stable and highly efficient
- the present invention is to provide a hot metal desulfurization method that can be desulfurized with a hot metal.
- the hot metal desulfurization method according to the first aspect of the present invention for solving the above problem is a hot metal desulfurization method using a mechanical stirring desulfurization apparatus, wherein the particle size is on the bath surface of the hot metal being stirred by a stirring blade.
- a desulfurization treatment is performed by adding a lime-based desulfurizing agent of 30 to 400 ⁇ m together with a carrier gas through an upper blowing lance to perform a desulfurization treatment.
- the upper blow lance is arranged facing downward in the vertical direction, the inner wall radius of the processing vessel containing the hot metal is D, and the radius of the stirring blade is R
- the radius (R) of the stirring blade is expressed by the following formula (1) with respect to the inner wall radius (D) of the processing vessel.
- the range satisfying the relationship, and the horizontal distance (A) satisfies the relationship of the following expression (2) with respect to the inner wall radius (D) and the radius (R) of the stirring blade. It is characterized by being within.
- R ⁇ (1/2) ⁇ D (1) R ⁇ A ⁇ (1/2) ⁇ D (2)
- D is the radius (m) of the inner wall of the processing vessel that contains the hot metal
- R is the radius (m) of the stirring blade
- A is the top blowing from the center of the processing vessel. The horizontal distance (m) to the center of the lance.
- the desulfurized slag generated in the desulfurization treatment using the lime-based desulfurizing agent is added to the hot metal bath surface in advance.
- the hot metal is stirred by the stirring blade, and then the desulfurizing agent is added.
- the lime-based desulfurization agent having a particle size of 30 to 400 ⁇ m is added by spraying from the top blowing lance, so that it does not contain fine powder that is easily scattered, and scattering during the spraying addition Is prevented.
- coarse particles with a small reaction interface area are not included, and the aggregation of the added desulfurizing agent is prevented, so that the desulfurization reaction interface area is increased and high-efficiency desulfurization treatment is realized stably. be able to.
- a reduction in the desulfurizing agent basic unit and a reduction in the amount of generated slag accompanying this can be achieved, resulting in an industrially beneficial effect.
- FIG. 1 is a schematic view of a mechanical stirring desulfurization apparatus used in the present invention.
- FIG. 2 is a diagram showing the relationship between the particle size (horizontal axis: mm) of the lime-based desulfurizing agent and the scattering rate (vertical axis:%).
- FIG. 3 is a diagram showing the relationship between the particle diameter of the lime-based desulfurizing agent (horizontal axis: mm) and the average diameter of the desulfurized slag (vertical axis: mm).
- FIG. 4 is a diagram showing the relationship between the particle size (horizontal axis: mm) of the lime-based desulfurization agent and the sulfur concentration in the hot metal after treatment (vertical axis: mass%).
- FIG. 1 shows a schematic view of a mechanical stirring type desulfurization apparatus used in the desulfurization test.
- a hot metal ladle 2 containing hot metal 3 discharged from a blast furnace is mounted on a carriage 1 and carried into a mechanical stirring type desulfurization apparatus.
- the mechanical stirring-type desulfurization apparatus includes a refractory stirring blade 4 that is immersed and buried in a hot metal 3 accommodated in a hot metal ladle 2 and swirls to stir the hot metal 3. It is moved up and down in a substantially vertical direction by an elevating device (not shown), and is turned around a shaft 4a as a rotating shaft by a rotating device (not shown).
- the mechanical stirring type desulfurization apparatus is provided with an upper blowing lance 5 for adding the lime-based desulfurizing agent 7 by blowing it upward toward the hot metal 3 accommodated in the hot metal ladle 2.
- the top blowing lance 5 is connected to a supply device including a dispenser 8 containing the powdered lime-based desulfurization agent 7 and a cutting device 9 for quantitatively cutting out from the dispenser 8. Therefore, the powdery lime-based desulfurizing agent 7 can be supplied together with the carrier gas 10 at an arbitrary timing.
- the carrier gas 10 a reducing gas, an inert gas, or a non-oxidizing gas is used.
- a dust collection hood (dust) 6 covering the hot metal ladle 2 is provided above the hot metal ladle 2, and exhaust gas being treated is exhausted through an exhaust duct (not shown) attached to the dust collection hood 6. Dust is sucked into a dust collector (not shown).
- the shaft 4a and the upper blowing lance 5 of the stirring blade 4 are installed so as to penetrate the dust collection hood 6 and move up and down.
- the particle size of the desulfurizing agent in the present invention is defined by sieving, and even if it has a spindle shape whose major axis is larger than the opening size of the sieving machine, as long as it passes through the sieving machine, It is defined as being smaller than the opening size of the sieve.
- the lime-based desulfurizing agent 7 used was adjusted in particle size to an average particle size of ⁇ 10%.
- a predetermined rotational speed 120 rpm
- the installation position of the top blowing lance 5 is the horizontal distance from the center of the hot metal ladle 2 to the center of the top blowing lance 5 with the inner wall radius (inner radius) of the hot metal ladle 2 being the processing vessel being D (m).
- Is A (m) the distance (A) is (1/2) ⁇ D, and the distance from the hot water surface of the hot metal 3 in the hot metal ladle to the tip of the top blowing lance 5 (referred to as “lance height”)
- the position was set to 1.0 m.
- the distance (A) was larger than the impeller radius (R) (m).
- the upper blowing lance 5 was arranged vertically downward at this position, and nitrogen gas was used as the carrier gas.
- the sieve As long as it passes through the divider, it is defined as being smaller than the opening size of the sieve.
- the method for measuring the average particle size of desulfurized slag is described in P8 to P12 of “Powder Engineering Series, Volume 1, Basic Physical Properties of Powder, Editor: Powder Industry Association, Publisher: Nikkan Kogyo Shimbun”. A weighted average based on the distribution standard r (0 (number), 1 (length), 2 (area), 3 (volume)) as 1 (ie, the distribution standard as the length) The particle size was measured.
- Fig. 2 shows the relationship between the particle size (horizontal axis: mm) of the lime-based desulfurizing agent and the scattering rate (vertical:%)
- Fig. 3 shows the particle size of the lime-based desulfurizing agent and the average diameter of the desulfurized slag (vertical axis). : Mm).
- the average diameter of the desulfurization slag increases as the particle diameter of the desulfurization agent increases, but the average diameter of the desulfurization slag does not become so large when the particle diameter of the desulfurization agent is 400 ⁇ m or less.
- the scattering rate is low, but the average diameter of the desulfurization slag becomes large, and an increase in the reaction interface area cannot be expected.
- FIG. 4 shows the relationship between the particle size of the lime-based desulfurizing agent and the sulfur concentration in the hot metal after treatment (vertical axis: mass%).
- the particle size of the lime-based desulfurizing agent 7 in the range of 30 to 400 ⁇ m, it may be possible to perform a stable desulfurization treatment up to the low-sulfur steel region. I understood.
- the particle size of the desulfurizing agent on the horizontal axis in FIGS. 2 to 4 indicates the average particle size of the desulfurizing agent with the particle size adjusted to an average particle size of ⁇ 10%.
- the present invention was made based on the above test.
- the lime-based desulfurization having a particle size of 30 to 400 ⁇ m on the bath surface of the hot metal being stirred by the stirring blade.
- the desulfurization treatment is performed by adding the agent and the carrier gas through the top blowing lance.
- a test for changing the installation position of the top blowing lance 5 in the radial direction of the hot metal ladle 2 using a lime-based desulfurizing agent 7 having a particle diameter of 30 to 400 ⁇ m was also carried out.
- the radius of the stirring blade 4 is R (m)
- the stirring blade radius (R) is equal to or less than 1/2 of the inner wall radius (D) of the hot metal ladle 2 (R ⁇ (1/2) ⁇ D).
- the upper blowing lance 5 is vertically downward, and the lance height is constant at 1.0 m.
- the position of the stirring blade 4 was set almost at the center of the hot metal pan 2.
- the horizontal distance (A) from the center of the hot metal ladle 2 to the center of the upper blowing lance 5 is changed from the outer peripheral position of the stirring blade 4, that is, the radius of the stirring blade (R) to 1 / of the inner wall radius (D) of the hot metal pan 2.
- the average value of the sulfur concentration in the hot metal after the desulfurization treatment is 0.0007% by mass (range of variation: 0.0006 to 0.001). 0015 mass%)
- the desulfurization agent scattering rate was 5 to 10%
- the particle size of the desulfurization slag was 5 to 10 mm, and stable and good results were obtained.
- the vortex formed by the stirring blade 4 forms a range in which the bath surface and the flow in the bath are directed downward in the vertical direction, and the desulfurization agent 7 is added to the range by blowing upward. This is because the desulfurization reaction proceeds by being caught inside. If it is too close to the center of the hot metal ladle 2, the desulfurizing agent 7 accumulates in the co-rotating part (the part of hot metal at the same speed with impeller) around the stirring blade 4 to form a lump. On the other hand, if it is too outside, the flow on the bath surface and in the bath is upward in the vertical direction, and it takes time to get caught in the bath, and during that time, scattering and aggregation progress.
- the upper blowing lance 5 is arranged in the vertically downward direction under the condition that the stirring blade radius (R) is within the range satisfying the relationship of the following expression (1) with respect to the inner wall radius (D) of the hot metal ladle 2.
- R ⁇ (1/2) ⁇ D
- R R ⁇ A ⁇ (1/2) ⁇ D
- D is the radius (m) of the inner wall of the processing vessel that contains the hot metal
- R is the radius (m) of the stirring blade
- A is the top blowing from the center of the processing vessel.
- the horizontal distance (m) to the center of the lance In operation, it is preferable to manage the scattering rate of the desulfurizing agent within a range of 40% or less and the desulfurized slag within a particle size of 14 mm or less according to the above conditions.
- the size of the stirring blade and the processing vessel may be determined according to the intended amount of hot metal treatment (generally 250 to 350 tons) and the required degree of stirring.
- R is preferably D / 3 or more from the viewpoint of stirring.
- a reducing gas As the carrier gas when the lime-based desulfurizing agent 7 is blown from the top blowing lance 5, a reducing gas, an inert gas or a non-oxidizing gas is used.
- the reducing gas include hydrocarbon gas
- examples of the inert gas include argon gas
- examples of the non-oxidizing gas include nitrogen gas.
- a reducing gas is the most suitable as a carrier gas among the above gases. That is, conveyance with a reducing gas is more advantageous than other gases because it reduces the oxygen partial pressure at the reaction interface and promotes the desulfurization reaction.
- the ideal low oxygen partial pressure at the hot metal-desulfurizing agent interface is realized.
- any substance can be used as long as it contains lime (CaO) as a main component, in other words, contains 50% by mass or more of CaO.
- lime CaO
- a mixture of Al 2 O 3 , CaF 2, or the like as a hatching promoter melting agent is used.
- dolomite CaO—MgO
- dolomite can also be used as the lime-based desulfurizing agent 7.
- the metal Al to be added (included when aluminum ash is used as a raw material, for example) is regarded as an active ingredient of an Al 2 O 3 source of a CaO—Al 2 O 3 -based lime-based desulfurizing agent.
- the recovered desulfurized slag is added onto the hot metal in the hot metal ladle 2 before starting the stirring of the hot metal 3 by the stirring blade 4, and the desulfurized slag added by stirring the hot metal 3 with the stirring blade 4 is wound into the hot metal.
- the recovered desulfurized slag is added to the hot metal 3 being stirred by the stirring blade 4 and the added desulfurized slag is wound into the hot metal. Thereafter, the addition of the lime-based desulfurizing agent 7 from the top blowing lance 5 may be started.
- the reason for starting the addition of the lime-based desulfurization agent 7 from the top blowing lance 5 after the desulfurization slag is wound into the hot metal is that the powdery lime-based desulfurization agent 7 added from the top blowing lance 5 is efficiently put into the hot metal. This is for infiltration. That is, the added desulfurization slag is present on the hot metal bath surface for a while even when the hot metal 3 is stirred by the stirring blade 4, and in this state, the desulfurizing agent from the top blowing lance 5 is transferred to the hot metal 3. This is because it prevents the intrusion of water.
- the time required for the added recovered slag to be caught in the hot metal varies depending on the equipment and operating conditions, but can be easily confirmed by visual observation.
- the molten iron discharged from the blast furnace is first subjected to desiliconization treatment and / or dephosphorization treatment.
- the slag containing iron oxide generated in the process is discharged, but it is difficult to completely discharge the slag from the container.
- the slag containing is left. That is, slag containing iron oxide remains in the hot metal ladle 2 before the desulfurization treatment is started.
- blast furnace slag and blast furnace cast floor desiliconization slag (desilication slag generated at blast furnace runner) flows into the hot metal ladle 2 and is brought to the desulfurization treatment process.
- the components in the slag brought to the desulfurization process that is, iron oxide contained in the desiliconization agent and dephosphorization agent, and SiO 2 contained in the desiliconization slag, dephosphorization slag and blast furnace slag are desulfurization reaction.
- Adversely affect That is, iron oxide is disadvantageous for the desulfurization reaction that is a reduction reaction, and SiO 2 coexists with CaO, which is the main component of the desulfurization agent, thereby reducing the basicity of the reaction site and reducing the desulfurization ability.
- the desulfurized slag collected in advance is added to the hot metal pan before the addition of the lime-based desulfurizing agent 7 to the hot metal 3, and the added desulfurized slag is stirred with the hot metal 3 to contain the remaining iron oxide.
- the slag or SiO 2 -containing slag is mixed with the added desulfurized slag, and the desulfurized slag adheres to the surface of the iron oxide-containing slag or SiO 2 -containing slag and is coated with the desulfurized slag.
- the present inventors when carrying out the desulfurization treatment after the desiliconization treatment, the present inventors add the desulfurization slag collected in advance into the hot metal ladle before starting the stirring of the hot metal 3 with the stirring blade 4, It has been confirmed that desulfurized slag mainly composed of SiO 2 and mainly CaO is produced at a high iron oxide concentration.
- the lime-based desulfurizing agent 7 having a particle size of 30 to 400 ⁇ m is added by spraying from the top blowing lance 5, so that scattering during spraying is prevented. At the same time, aggregation of the added desulfurizing agent is prevented, the desulfurization reaction interfacial area is increased, and high-efficiency desulfurization treatment is stably realized.
- the particle size of the lime-based desulfurization agent is in the range of 20 ⁇ m or less (Comparative Example 1), in the range of 500 to 1000 ⁇ m (Comparative Example 2), in the range of 200 to 400 ⁇ m (Invention Example 1), and 30 to 100 ⁇ m.
- Comparative Examples 1 and 2 and Invention Examples 1 and 2 the installation position of the top blowing lance is placed in a range that satisfies the above-mentioned formula (2), and desulfurization reaction is performed. The effect of the particle size of the desulfurizing agent on the flow rate was investigated.
- Example 5 of the present invention the installation position of the top blowing lance was installed in a range satisfying the above expression (2), and the desulfurized slag collected in advance was added onto the hot metal before the stirring blades were rotated.
- Other operating conditions other than the particle size of the lime-based desulfurizing agent and the position where the top blowing lance was installed were in accordance with Table 1. All tests were conducted with 100 charges (ch). Table 2 shows the operation conditions and the operation results.
- Examples 6 to 9 of the present invention are d / 3 ⁇ R ⁇ d / 2 + 1/3 ⁇ (D ⁇ d) (in the symbol of the present invention, (2R) where the position of the top lance is suitable in Patent Document 1. / 3 ⁇ A ⁇ R + (1/3) ⁇ (2D ⁇ 2R), and the right side satisfies (2D) / 3 + R / 3), but R ⁇ A ⁇ (1 / 2) xD is an unsatisfactory test.
- the desulfurization efficiency is improved as compared with Comparative Example 3 which is a conventional addition method, but in Inventive Examples 10 and 11 which are preferred ranges of the present invention, The desulfurization efficiency is remarkably improved. That is, as seen in the maximum S concentration after the treatment and the ratio of S ⁇ 0.003% by mass, Example 10 and Example 11 achieve low sulfidation with very small variations. . [Example 3]
- the desulfurization treatment was performed under various conditions shown in Table 4, and the obtained results are also shown in Table 4.
- the operating conditions other than those shown in Table 4 were the same as in Example 1.
- Example 12 to 16 of the present invention in Table 4 the influence of the stirring time from when the recycled desulfurized slag (recovered slag) was charged in advance until the start of addition of the desulfurizing agent from the top blowing lance was confirmed.
- Examples 17 to 22 of the present invention the influence of the mixed amount of Al 2 O 3 in the CaO—Al 2 O 3 -based desulfurizing agent was confirmed.
- Examples 23 and 24 of the present invention the influence of the carrier gas of the desulfurizing agent was confirmed. did.
- the amount of Al 2 O 3 mixed in the CaO—Al 2 O 3 desulfurizing agent is 10 to 30% (internal weight%). Was found to be particularly suitable. Further, from Invention Example 23 and Invention 24, it can be confirmed that the use of a reducing gas (propane gas (hydrocarbon gas) of Invention Example 24) as the carrier gas further improves the desulfurization efficiency. It was.
- a reducing gas propane gas (hydrocarbon gas) of Invention Example 24
- high-efficiency desulfurization treatment that is, treatment such that S after desulfurization treatment is, for example, 0.003% by mass
- S after desulfurization treatment is, for example, 0.003% by mass
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Abstract
Description
d/3≦R≦d/2+1/3×(D−d)
の関係を満足させる((2)式:ただしDは溶銑を収容する処理容器の内径(直径)、dは攪拌羽根の直径)ことが好ましいとしている([0017]~[0020]段落)。 In order to solve this problem, Patent Document 1 discloses that in a hot metal desulfurization method using a mechanical stirring type desulfurization apparatus, a desulfurizing agent is placed on the bath surface of the hot metal being stirred by a stirring blade via an upper blowing lance. Thus, a method of performing a desulfurization process by blasting with a carrier gas has been proposed. According to Patent Document 1, since a fine-sized desulfurization agent having excellent reactivity is added together with a carrier gas, scattering during addition is reduced, and the addition yield of the desulfurization agent is improved. The fine-grain desulfurization agent has a large reaction interface area, and therefore, the desulfurization reaction is promoted, and the desulfurization rate can be remarkably improved. Further, in Patent Document 1, from the viewpoint of smoothly dispersing the sprayed desulfurizing agent in the hot metal, the horizontal distance R from the center of the stirring blade to the spraying position of the desulfurizing agent,
d / 3 ≦ R ≦ d / 2 + 1/3 × (D−d)
(Equation (2): where D is the inner diameter (diameter) of the processing vessel containing the hot metal, and d is the diameter of the stirring blade) (paragraphs [0017] to [0020]).
R≦(1/2)×D …(1)
R≦A≦(1/2)×D …(2)
但し、(1)式及び(2)式において、Dは、溶銑を収容する処理容器の内壁半径(m)、Rは、攪拌羽根の半径(m)、Aは、処理容器の中心から上吹きランス中心までの水平距離(m)である。 In the hot metal desulfurization method according to the second invention, in the first invention, the upper blow lance is arranged facing downward in the vertical direction, the inner wall radius of the processing vessel containing the hot metal is D, and the radius of the stirring blade is R When the horizontal distance from the center of the processing vessel to the center of the upper blowing lance is A, the radius (R) of the stirring blade is expressed by the following formula (1) with respect to the inner wall radius (D) of the processing vessel. The range satisfying the relationship, and the horizontal distance (A) satisfies the relationship of the following expression (2) with respect to the inner wall radius (D) and the radius (R) of the stirring blade. It is characterized by being within.
R ≦ (1/2) × D (1)
R ≦ A ≦ (1/2) × D (2)
However, in the formulas (1) and (2), D is the radius (m) of the inner wall of the processing vessel that contains the hot metal, R is the radius (m) of the stirring blade, and A is the top blowing from the center of the processing vessel. The horizontal distance (m) to the center of the lance.
R≦(1/2)×D …(1)
R≦A≦(1/2)×D …(2)
但し、(1)式及び(2)式において、Dは、溶銑を収容する処理容器の内壁半径(m)、Rは、攪拌羽根の半径(m)、Aは、処理容器の中心から上吹きランス中心までの水平距離(m)である。
操業においては上記条件等により、脱硫剤の飛散率を40%以下、脱硫スラグを粒径14mm以下の範囲にそれぞれ管理することが好ましい。 なお、攪拌羽根4(および回転軸)を処理容器の中心に位置させることは必須ではなく、偏心させても攪拌に問題は無い。
また、攪拌羽根や処理容器のサイズは、目的とする溶銑処理量(一般に250~350トン)および必要とされる攪拌の程度に応じて決定すればよい。 目安としえては、Rは攪拌の観点からD/3以上であることが好ましい。 That is, the
R ≦ (1/2) × D (1)
R ≦ A ≦ (1/2) × D (2)
However, in the formulas (1) and (2), D is the radius (m) of the inner wall of the processing vessel that contains the hot metal, R is the radius (m) of the stirring blade, and A is the top blowing from the center of the processing vessel. The horizontal distance (m) to the center of the lance.
In operation, it is preferable to manage the scattering rate of the desulfurizing agent within a range of 40% or less and the desulfurized slag within a particle size of 14 mm or less according to the above conditions. In addition, it is not essential to position the stirring blade 4 (and the rotation shaft) at the center of the processing container, and there is no problem in stirring even if it is decentered.
Further, the size of the stirring blade and the processing vessel may be determined according to the intended amount of hot metal treatment (generally 250 to 350 tons) and the required degree of stirring. As a guide, R is preferably D / 3 or more from the viewpoint of stirring.
また、脱硫処理工程が第1工程の場合でも、高炉スラグや高炉鋳床脱珪スラグ(desiliconization slag generated at blast furnace runner)が溶銑鍋2に流入し、脱硫処理工程に持ち来たされる。 この場合、脱硫処理工程に持ち来たされるスラグ中の成分、すなわち脱珪剤及び脱燐剤に含まれる酸化鉄や、脱珪スラグ、脱燐スラグ、高炉スラグに含まれるSiO2が脱硫反応に悪影響を及ぼす。
即ち、酸化鉄は還元反応である脱硫反応に不利であり、またSiO2は脱硫剤の主成分であるCaOと共存することで、反応サイトの塩基性低下を招き脱硫能を低下させる。 In general, the molten iron discharged from the blast furnace is first subjected to desiliconization treatment and / or dephosphorization treatment. After the desiliconization process and / or the dephosphorization process, the slag containing iron oxide generated in the process is discharged, but it is difficult to completely discharge the slag from the container. The slag containing is left. That is, slag containing iron oxide remains in the
Even when the desulfurization treatment process is the first process, blast furnace slag and blast furnace cast floor desiliconization slag (desilication slag generated at blast furnace runner) flows into the
That is, iron oxide is disadvantageous for the desulfurization reaction that is a reduction reaction, and SiO 2 coexists with CaO, which is the main component of the desulfurization agent, thereby reducing the basicity of the reaction site and reducing the desulfurization ability.
特に、上吹きランス5により脱硫剤を浴面に投射する場合には脱硫スラグの添加効果がより顕著になる。
尚、本発明者らは、脱珪処理後に脱硫処理を実施する場合に、予め回収した脱硫スラグを攪拌羽根4による溶銑3の攪拌開始前に溶銑鍋内に添加することで、中心部は、酸化鉄濃度が高くSiO2を主体とし、その周囲は、CaOを主体とする脱硫スラグが生成されることを確認している。 That is, by adding the previously recovered desulfurized slag, the supply of oxygen from the remaining iron oxide-containing slag to the
In particular, when the desulfurizing agent is projected onto the bath surface by the
In addition, when carrying out the desulfurization treatment after the desiliconization treatment, the present inventors add the desulfurization slag collected in advance into the hot metal ladle before starting the stirring of the
[実施例2] As shown in Table 2, compared with Comparative Example 1 and Comparative Example 2, in Invention Example 1 and Invention Example 2, the average sulfur concentration of the hot metal after the desulfurization treatment decreased. Further, the present invention example 3 and the present invention example 4 in which the installation position of the top blowing lance is outside the preferred range and the present invention example 2 in which the installation position of the top blowing lance is in a suitable range are compared. It was found that the desulfurization efficiency at 2 was high. Furthermore, in Invention Example 5 in which desulfurized slag was recycled, it was confirmed that the average sulfur concentration of the hot metal after the desulfurization treatment was further reduced and the variation was reduced.
[Example 2]
[実施例3] Examples 6 to 9 of the present invention are d / 3 ≦ R ≦ d / 2 + 1/3 × (D−d) (in the symbol of the present invention, (2R) where the position of the top lance is suitable in Patent Document 1. / 3 ≦ A ≦ R + (1/3) × (2D−2R), and the right side satisfies (2D) / 3 + R / 3), but R ≦ A ≦ (1 / 2) xD is an unsatisfactory test. In Inventive Examples 6 to 9, the desulfurization efficiency is improved as compared with Comparative Example 3 which is a conventional addition method, but in Inventive Examples 10 and 11 which are preferred ranges of the present invention, The desulfurization efficiency is remarkably improved. That is, as seen in the maximum S concentration after the treatment and the ratio of S <0.003% by mass, Example 10 and Example 11 achieve low sulfidation with very small variations. .
[Example 3]
なお、上記実施例で使用した以外の周知の脱硫剤、搬送ガスにおいてもとくに問題なく本発明の効果が得られることを確認したが、発明効果の観点からは、脱硫剤としてCaO−Al2O3系脱硫剤を使用することが有利であった。 In addition, from Examples 17 to 22 of the present invention, in the mechanical stirring type desulfurization apparatus used in this example, the amount of Al 2 O 3 mixed in the CaO—Al 2 O 3 desulfurizing agent is 10 to 30% (internal weight%). Was found to be particularly suitable. Further, from Invention Example 23 and Invention 24, it can be confirmed that the use of a reducing gas (propane gas (hydrocarbon gas) of Invention Example 24) as the carrier gas further improves the desulfurization efficiency. It was.
Incidentally, known desulfurizing agent other than those used in the above embodiment, it was confirmed that the effect of the present invention without particular problems in the transportation gas is obtained, in terms of the invention effects, CaO-Al 2 O as a desulfurizing agent It was advantageous to use a 3 system desulfurizing agent.
2 溶銑鍋(処理容器)
3 溶銑
4 攪拌羽根
4a 回転羽根の軸
5 上吹きランス
6 集塵フード
7 石灰系脱硫剤
8 ディスペンサー
9 切り出し装置
10 搬送用ガス
A 処理容器の中心から上吹きランスの中心までの水平距離
R 攪拌羽根の半径
D 処理容器の内壁半径 1
3
Claims (3)
- 機械攪拌式脱硫装置を用いた溶銑の脱硫方法において、攪拌羽根によって攪拌されている溶銑の浴面上に、粒径が30~400μmの石灰系脱硫剤を、上吹きランスを介して搬送用ガスとともに上吹き添加して脱硫処理を行う、溶銑の脱硫方法。 In a hot metal desulfurization method using a mechanical stirring desulfurization apparatus, a lime-based desulfurization agent having a particle size of 30 to 400 μm is conveyed on the bath surface of the hot metal being stirred by a stirring blade through a top blowing lance. A hot metal desulfurization method in which the desulfurization treatment is performed by top blowing.
- 前記上吹きランスは鉛直方向下方を向いて配置され、溶銑を収容する処理容器の内壁半径をD、攪拌羽根の半径をR、処理容器の中心から前記上吹きランス中心までの水平距離をAとしたときに、前記攪拌羽根の半径(R)が前記処理容器の内壁半径(D)に対して下記の(1)式の関係を満足する範囲内であって、且つ、前記水平距離(A)が、前記内壁半径(D)及び前記攪拌羽根の半径(R)に対して下記の(2)式の関係を満足する範囲内である、請求項1に記載の溶銑の脱硫方法。
R≦(1/2)×D …(1)
R≦A≦(1/2)×D …(2)
但し、(1)式及び(2)式において、Dは、溶銑を収容する処理容器の内壁半径(m)、Rは、攪拌羽根の半径(m)、Aは、処理容器の中心から上吹きランス中心までの水平距離(m)である。 The upper blowing lance is arranged vertically downward, the inner wall radius of the processing vessel containing hot metal is D, the radius of the stirring blade is R, and the horizontal distance from the center of the processing vessel to the center of the upper blowing lance is A. The radius (R) of the stirring blade is within a range satisfying the relationship of the following expression (1) with respect to the inner wall radius (D) of the processing vessel, and the horizontal distance (A) The hot metal desulfurization method according to claim 1, wherein is within a range satisfying a relationship of the following expression (2) with respect to the inner wall radius (D) and the radius (R) of the stirring blade.
R ≦ (1/2) × D (1)
R ≦ A ≦ (1/2) × D (2)
However, in the formulas (1) and (2), D is the radius (m) of the inner wall of the processing vessel that contains the hot metal, R is the radius (m) of the stirring blade, and A is the top blowing from the center of the processing vessel. The horizontal distance (m) to the center of the lance. - 予め回収した、石灰系脱硫剤による脱硫処理にて発生した脱硫スラグを、前記溶銑の浴面上に添加した後に前記攪拌羽根によって溶銑を攪拌し、その後、前記脱硫剤を添加する、請求項1または請求項2に記載の溶銑の脱硫方法。 The desulfurization slag generated in the desulfurization treatment with a lime-based desulfurization agent, which has been collected in advance, is added to the hot metal bath surface, the hot metal is stirred with the stirring blade, and then the desulfurization agent is added. Alternatively, the hot metal desulfurization method according to claim 2.
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