WO2009152643A1 - 用于炉外精炼脱磷、脱硫、去除细小杂物的添加剂及其制法和应用 - Google Patents

用于炉外精炼脱磷、脱硫、去除细小杂物的添加剂及其制法和应用 Download PDF

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WO2009152643A1
WO2009152643A1 PCT/CN2008/001191 CN2008001191W WO2009152643A1 WO 2009152643 A1 WO2009152643 A1 WO 2009152643A1 CN 2008001191 W CN2008001191 W CN 2008001191W WO 2009152643 A1 WO2009152643 A1 WO 2009152643A1
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powder
calcium
additive
mixture
carbonate
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PCT/CN2008/001191
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English (en)
French (fr)
Inventor
唐复平
王晓峰
刘万山
孟劲松
任子平
李德刚
陈本文
王仁贵
张军
王文仲
李镇
张晓军
孙群
栗红
常桂华
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鞍钢股份有限公司
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Priority to PCT/CN2008/001191 priority Critical patent/WO2009152643A1/zh
Publication of WO2009152643A1 publication Critical patent/WO2009152643A1/zh

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    • 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
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62802—Powder coating materials
    • C04B35/62805—Oxide ceramics
    • 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
    • C21C7/0075—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
    • C21C7/064—Dephosphorising; Desulfurising
    • C21C7/0645—Agents used for dephosphorising or desulfurising
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
    • C04B2235/445—Fluoride containing anions, e.g. fluosilicate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • 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
    • C21C7/0056—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires
    • C21C2007/0062—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 using cored wires with introduction of alloying or treating agents under a compacted form different from a wire, e.g. briquette, pellet

Definitions

  • the invention relates to an external refining process of various microalloyed steels and special steels, in particular to an additive for refining dephosphorization, desulfurization and removing fine inclusions outside a molten steel furnace, and a preparation method and application thereof.
  • the preferred additive and application process for dephosphorization, desulfurization and removal of fine inclusions in microalloyed steel or special steel refining are particularly preferred.
  • this indicator may not meet the requirements at all.
  • the steel cord requires A1 2 0 3 inclusions less than 10 ⁇ 15 ⁇ to meet the 200,000 meters in the drawing process. Decapitation requirements.
  • the desulfurization and dephosphorization of molten steel are carried out.
  • the current desulfurization uses a CaO-Al 2 0 3 based steel furnace external desulfurizer, and the dephosphorization uses a CaO-FeO based steel dephosphorization refining agent.
  • the defects are: CaO-Al 2 0 3 based steel furnace desulfurization refining agent can only desulfurize, can not dephosphorize;
  • the dephosphorization refining agent outside the CaO-FeO-based steel water furnace not only has a poor dephosphorization effect, but also the molten steel is seriously returned to phosphorus after refining and reducing the slag, which pollutes the molten steel and affects production.
  • Most of the inclusions in the molten steel are naturally floated by buoyancy, which can be said to have been carried out throughout the metallurgical process.
  • buoyancy which can be said to have been carried out throughout the metallurgical process.
  • steelmaking is a large-scale continuous production.
  • the natural floating efficiency is very low and cannot meet the production requirements. Therefore, special means such as refining and filtration outside the furnace are often used to enhance the removal of inclusions.
  • Argon blowing is one of the important refining methods for ladle. Bottom blowing argon can uniform the composition and temperature of molten steel. The most important function is to promote the removal of inclusions in molten steel.
  • the above method can reduce the phosphorus and sulfur content in the molten steel to some extent and remove the inclusions, it can not effectively control the phosphorus, sulfur and fine inclusions in the steel at the same time.
  • the invention provides an additive capable of stably controlling the phosphorus and sulfur content in the molten steel and the size and quantity distribution of the inclusions in the above-mentioned prior art, and the effect is obvious and stable, and the quality of the refined steel is ensured and improved. Reduce smelting costs, and the preparation process is simple, a variety of dosage forms are conducive to use, operation, transportation and storage.
  • Another object of the invention is the use of the additive in the refining of molten steel.
  • an additive for refining dephosphorization, desulfurization, and removal of fine inclusions which is a composite sphere composed of a core and an outer shell, the core of which is mainly low A melting point pre-slag powder, calcium carbonate, magnesium carbonate or a mixture of calcium carbonate and magnesium carbonate, the outer shell consisting essentially of a mixture of one or both of calcium oxide or magnesium oxide.
  • the core is prepared from the following raw materials in percentage by weight:
  • the core is prepared from the following raw materials in percentage by weight: Low melting point pre-slag powder 10% ⁇ 50% calcium carbonate, magnesium carbonate or a mixture of calcium carbonate and magnesium carbonate 10% ⁇ 45%
  • the low melting point slag powder by the following pre-feed was prepared by a percentage by weight: CaO 10% ⁇ 70%, A1 2 0 3 15% ⁇ 50%, Si0 2 0 ⁇ 10%, MgO 0 ⁇ 10%, CaF 2 0 ⁇ 30 %, its melting point is 1100 ° (: ⁇ 1550 ° C.
  • the outer casing also includes 0 to 20% of a binder.
  • An additive for refining dephosphorization, desulfurization, and removal of fine inclusions mainly consisting of low melting point premelted slag powder, calcium carbonate, magnesium carbonate or a mixture of calcium carbonate and magnesium carbonate, and one or two of calcium oxide or magnesium oxide.
  • the additive is prepared from the following raw materials in percentage by weight:
  • the additive is characterized in that it is mainly prepared from the following raw materials by weight: percentage: low melting point premelted powder 10% ⁇ 50% calcium carbonate, magnesium carbonate or a mixture of calcium carbonate and magnesium carbonate 10% ⁇ 45 % Calcium oxide or magnesium oxide or a mixture of calcium oxide and magnesium oxide 30 ⁇ / ⁇ ⁇ 70% Calcium fluoride 5% ⁇ 30%
  • the raw material has a particle size of from 1 nm to 3.5 mm, wherein the activity of the calcium oxide and the magnesium oxide is SOOmL, and the additive further comprises a core-line dosage form.
  • the binder is any one or a mixture of two or more of clay, ordinary cement, bentonite, and water glass.
  • the process method of the additive comprises the following steps:
  • shell mixing According to the ratio, the raw materials required for the outer shell are thoroughly mixed in the mixer.
  • the activity of calcium oxide and magnesium oxide is 200 ml, and the mixing time is 1 1! ⁇ 3h spare.
  • compounding the above-mentioned prepared core and shell material are compositely ball-formed on a ball-making device by a rolling method, wherein the prepared composite sphere has a size of 20 to 80 mm; the diameter of the prepared composite pellet is controlled at 0.25 ⁇ 20mm.
  • overall drying The composite spheres and pellets prepared in the above steps are dried in a dryer, and the drying temperature is 60° (: ⁇ 200 ° C, time is 101! ⁇ 24h, finished product) Packaging.
  • the preparation method of the additive comprises the following steps:
  • the particle size is Inn! ⁇ 3.5mm low melting point pre-slag powder, calcium fluoride, calcium carbonate, magnesium carbonate or a mixture of calcium carbonate and magnesium carbonate, calcium oxide, magnesium oxide or a mixture of calcium oxide and magnesium oxide and binder into the mixer Mix well and mix in the mixture, mixing time 11! ⁇ 8 ho
  • Drying treatment The above prepared powder is dried in a drying apparatus at 80 ° C ⁇ 200 ° C for 21 hours! ⁇ 24h is the finished powder.
  • the preparation method of the additive further comprises the following steps:
  • a low carbon steel strip with a thickness of 2mm ⁇ 5 mm is used as the outer skin of the core wire to prepare
  • the finished powder is the core of the wire-making machine, and the single-layer steel belt is used to make the core wire, the wire speed is 8 ⁇ 30m/min, and the powder content of the core wire is 100 ⁇ 240g/m, which is the finished product, packaging. .
  • the additive is used in dephosphorization, desulfurization and removal of fine inclusions in the refining process outside the furnace.
  • the additive of the present invention is capable of dephosphorization, desulfurization and removal of fine inclusions in the refinery production process of various microalloyed steels and special steels, and is realized by DF, RH, VD, CAS-OB tundish or Feeding in the crystallizer can stably control the size and distribution of phosphorus, sulfur and inclusions in the molten steel, and achieve the desired effect.
  • the invention adopts an ultrafine powder of calcium carbonate, magnesium carbonate or a mixture of calcium carbonate and magnesium carbonate as an in-situ generating agent for microbubbles.
  • the decomposition process of calcium carbonate and magnesium carbonate is as follows:
  • the size of the bubbles generated is comparable to the size of the powder. Therefore, it is possible to introduce ultrafine bubbles (the size of the bubbles is between 10 and 300 m) in the molten steel. The smaller the size of the bubble, the higher the removal efficiency of the inclusions.
  • a product of magnesium oxide or calcium oxide is small in size and can be rapidly melted in molten steel to form slag droplets and form a low-melting calcium aluminate with ⁇ 1 2 3 inclusions in the molten steel, which is easy to float up into the ladle slag, thereby reducing refining number and size of the inclusions ⁇ 1 2 0 3 produced.
  • Lime dephosphorization solvent as a fixing agent in the presence of calcium oxide in the form of highly active, highly active calcium oxide after rapid melting, i.e. form 3CaO * P 2 0 5 or 4CaO 'P 2 0 5 and ⁇ 2 0 5, P may be fixed And discharged into the slag.
  • 2CaO+2S 2CaS+0 2
  • oxygen generated by the reaction combines with silicon in the molten steel to produce silicon dioxide (Si0 2 ).
  • the silica forms dicalcium silicate, and the dicalcium silicate forms a solid layer encased on the surface of the lime powder.
  • Feeding fine calcium oxide powder can be shorter The time is fully reacted to avoid the formation of dicalcium silicate on the surface of the calcium oxide, which improves the utilization of the active calcium oxide powder.
  • the invention is scientific and reasonable, and when it is added into the molten steel to generate fine bubbles, the collision probability with the inclusions is high, and the fine slag droplets have the function of slag washing, and can also effectively treat the inclusions in the molten steel.
  • the additive of the invention has the multifunctional function, can not only dephosphorize and desulfurize, but also effectively control the quantity size and distribution of fine inclusions in the molten steel, and the additive of the invention can be used to increase the total oxygen in the steel.
  • the content of sulfur and phosphorus is controlled at 3-15ppm, 5-30ppm and 10-50ppm respectively, and the equivalent diameter of inclusions is 0.3-5 ⁇ .
  • the preparation process is simple, flexible and convenient, and the dosage form is more suitable for application.
  • Feeding, dusting, shot peening and even ball-shaped direct input are fed in LF, RH, VD, CAS-OB, tundish or crystallizer, which is easy to operate; at the same time, the purity of molten steel is obviously improved to reduce the smelting cost.
  • Preparation of low-melting pre-melted slag take CaCO powder 40kg, A1 2 0 3 powder 35 kg, Si0 2 powder 10 kg, ⁇ 3 ⁇ 40 powder 1013 ⁇ 4, CaF 2 powder 5 kg into the mixer and evenly Mix the mixture, then melt it in the magnesite, cool it, and then grind it into a particle size of Inn! ⁇ 3.5mm powder, its melting point is reserved at 1100 ⁇ 1550 °C; then the low melting point pre-melted slag powder 35 kg and calcium fluoride powder 5 kg with particle size of 1 nm ⁇ 3.5mm are taken according to the formula ratio.
  • the powder is used in the wire making machine, and the single-layer steel belt is used to make the core wire, the core speed is 8 ⁇ 30m/min, the powder content of the core wire is 100 ⁇ 240g/m, and the volume is 1000 ⁇ 2000m/volume. Convenient to control the amount of addition and the speed of addition, the cross section of the core wire is round, the package should ensure good sealing, prevent moisture, and use within 20 days.
  • the method of preparing low-burning pre-melting powder by taking CaO70 kg, Al 2 0 3 15 kg, Si0 2 3 kg, MgO 2 kg and CaF 2 10 kg according to the formula ratio is the same as that in the first embodiment; 45 kg of slag powder, 30 kg of calcium carbonate and magnesium carbonate (the ratio of the two is not strict), 10 kg of mixture of calcium oxide and cerium oxide, 15 kg of binder; core according to the above ratio
  • the required solid raw materials are crushed and crushed, and at the same time, the airflow is micromilled to achieve a particle size of 80 ⁇ ! ⁇ 3mm, the above-mentioned core powder is placed in the mixer for thorough mixing and mixing, and the mixing time is l ⁇ 3h.
  • the mixed raw materials are dried in a drying apparatus, and the drying temperature is 100 to 140 ° C, and the time is 2 to 4 h.
  • the powder after the above drying treatment is made into a core on a ball press by an extrusion method, and the control of the size of the core is determined by sieving, and the diameter of the core is 0.05 to 40 mm.
  • the powder required for taking the outer casing according to the above ratio is thoroughly mixed in the mixer, the activity of calcium oxide is 200 ml, and the mixing time is l ⁇ 3 h.
  • the prepared core and the shell material are compositely ball-formed on a disc pelletizer by a rolling method, and the size of the sphere is controlled by screening, and the prepared composite sphere has a size of 20 to 80 mm, and finally the composite sphere is Drying at 90 ⁇ 160°C, drying time 10 ⁇ 15h, cooling to room temperature, respectively, packing 10 kg ⁇ 30kg/bag and using it within 20 days.
  • Example 4 According to the formulation ratio, CaO50 kg, Al 2 O 3 40 kg, Si0 2 5 kg, MgO 5 kg, the method for preparing the low melting point premelted slag powder is the same as in the first embodiment; the prepared low melting point premelted slag powder is 60 kg.
  • Example 2 calcium fluoride 10 kg, calcium carbonate 1 kg, magnesium oxide 25 k g , binder 4 kg and the same method as in Example 1 to prepare a powder; according to the above ratio, the solid raw material required for the core is crushed and crushed, At the same time, the airflow micro-grinding grinding is used to reach the particle size of lnm ⁇ : L.5mm, and the above-mentioned core powder is put into the mixer for thorough mixing and mixing, and the mixing time is l ⁇ 3h.
  • the mixed raw materials are further dried in a drying apparatus, and the drying temperature is 80 to 110 ° C, and the time is 2 to 6 hours.
  • the raw material after the drying treatment is made into a core on a ball press by an extrusion method, and the control of the size of the core is determined by sieving, and the diameter of the core is 0.05 to 40 mm.
  • the powder required for taking the outer casing according to the above ratio is thoroughly mixed in the mixer, the activity of calcium oxide is 200 ml, and the mixing time is l ⁇ 3 h.
  • the prepared core and the shell material are compositely pelletized by a rolling method on a disc granulator, and the size of the pellet is controlled by sieving, and the size of the prepared composite pellet is 0.25 to 20 mm, and finally Dry at 60 ⁇ 120 °C, drying time is 10 ⁇ 18h, cool it to room temperature and pack it 10 ⁇ 30kg/bag separately, and use it within 20 days.
  • the method for preparing the low melting point premelted slag powder is the same as in the first embodiment; taking the prepared low melting point premelted slag powder 3 kg, calcium fluoride 2 kg, 10 kg of calcium carbonate, and 85 kg of magnesium oxide were powdered and dried in the same manner as in Example 1. After the low carbon steel strip having a thickness of 2 mm was used as the sheath of the cored wire, the core was the dried powder. On the wire making machine, a core wire was prepared in the same manner as in Example 2, and packaged into a 1000 m/roll, which had a square cross section and was used within 20 days.
  • Calcium fluoride 18 kg, magnesium carbonate 55 kg, calcium oxide 15 kg, binder 10 kg, powder was prepared in the same manner as in Example 1 except that the particle size of the raw materials used was 0.01 mm to 0.8 mm; The same method is used to make the composite pellets, and the size of the pellets is controlled by screening, and the diameter is controlled in the range of 5 mm to 15 mm, at 90 Dry at °C ⁇ 120°C for 10 ⁇ 15h, cool to room temperature and pack 500kg/bag and use within 20 days.
  • Example 6 Take 20 parts of the low-melting pre-melted slag powder of Example 6 and grind it into 20 kg of magnesium carbonate powder with a particle size of 1 to 50 nm, and the particle size of the remaining raw materials is between 0.4 mm and 3.4 mni, and calcium oxide 40 kg. 20 kg of binder was uniformly mixed to prepare a powder.
  • the composite sphere was prepared in the same manner as in Example 3. The size of the sphere was controlled by screening, and the diameter was controlled at 30 mm to 60 mm; at 100 ° C to 200 ° Dry in °C drying equipment for 10h ⁇ 24h, cool to room temperature and pack into 1000kg/bag and use within 20 days.
  • the binders described in Examples 1 to 7 are one or a mixture of two or more of clay, ordinary cement, bentonite, and water glass.
  • the powder is sprayed in the LF, RH or CAS-OB refining stage, and the conveying pressure is controlled at 0.01 ⁇ 1.5MPa.
  • the additive of the invention is 0.5 ⁇ 5kg/t, and the conveying amount of the powder is 0.01 ⁇
  • the additive When the additive is added to the molten steel, the calcium carbonate and the magnesium carbonate powder are sufficiently small to produce fine and small bubbles, and the smaller the bubbles, the higher the removal efficiency of the inclusions, and at the same time, the finer the particle size of the active calcium oxide is.
  • the steel is transported to the LF station, the temperature is sampled and the composition is adjusted.
  • the core wire is fed from the LF station to the core wire, and the argon mixing is stopped during the feeding process, and the feeding speed is 150 ⁇ 350m / min, the feeding amount is 0.1 ⁇ 2.4kg / t, after the feeding line is still l ⁇ 5min, the argon blowing is lightly treated, the pressure is 0.13 ⁇ 0.8 1 ⁇ 3 ⁇ 4
  • the flow rate of argon is 50 ⁇ 120 / 1 1 1, weak
  • the argon blowing time is 3 ⁇ 5min, and the argon blowing is finished. That is to say, the continuous casting is carried out by continuous casting. It is also possible to feed the wire on the RH down pipe side.
  • the feeding speed is 180 ⁇ 350m/min, the feeding amount is 0.5 ⁇ 4.5kg/t, the RH cycle time after feeding the line is 3 ⁇ 10min, and the pouring is carried out immediately after the end of the cycle.
  • the casting is cast in full protection.
  • the morphology and particle size of the inclusions were analyzed under a microscope of 500 times along the inner arc of the slab, and the area of the inclusions was analyzed by quantitative metallography (analytical area: lOX lOmm), and the total oxygen content was analyzed by nitrous oxide. , using chemical analysis method to determine the S and P content analysis results are shown in Table 1.
  • the additive of the present invention achieves satisfactory effects in dephosphorization, desulfurization and removal of impurities in various microalloyed steels and special steel refining, and improves the refining quality of the steel.
  • the new height provides a preferred multi-functional additive and effectively reduces smelting costs.
  • the cored wire is fed into the molten steel at a feeding speed of 200 to 350 m/min and a feeding amount of 0.5 to 4.5 kg/t.
  • argon gas is stirred at the bottom, the argon gas intensity is 0.001 ⁇ 0.004m 3 /rnin-t, the argon blowing time is l ⁇ 10min, the continuous casting adopts the whole process of protective casting; or the steel package is fed to the VD station immediately after feeding.
  • Feed the core wire directly into the tundish the feeding position is below the long nozzle, the feeding speed is 200 ⁇ 350m/min, the feeding amount is l ⁇ 3kg/t; or the core wire is directly fed into the crystallizer, Feed speed The amount added is the same as that fed from the tundish.
  • the pellets are fed into the molten steel by blasting equipment in LF, RH, VD, CAS-OB, tundish or crystallizer, using argon as the carrier, the gas pressure is controlled at 0.1 ⁇ 1.0 MPa, and the injection amount is 0.5 ⁇ 5kg. /t. Continuous casting is fully protected and cast.
  • the temperature is sampled.
  • the actual temperature of the molten steel in the smelting process is higher than the normal production temperature by 5 ⁇ 10 °C, and the composition is adjusted.
  • the vacuum degree of the vacuum chamber is 80 ⁇ 300Pa.
  • the alloy silo is put into the composite spherical additive, the amount is 0.8 ⁇ 2.5kg/t, the single addition amount is 50 ⁇ 130kg, the interval between the two additions is l ⁇ 5min; the sphere is added after the circulation is l ⁇ 10min; continuous casting Full-scale protection casting.
  • the spherical additive has a compressive strength of 5 to 35 MPa, high thermal stability, and a delayed bursting time of 1600 ° C for more than 10 s.
  • the morphology and particle size of the inclusions were analyzed under a 500-fold microscope along the inner arc of the casting slab, and the area of the inclusions was analyzed by quantitative metallography (analytical area: 10 ⁇ 10 mm), and the total oxygen was analyzed by nitrous oxide.
  • the content, the chemical analysis method for the determination of S, P content analysis results are shown in Table 2.

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Description

用于炉外精炼脱磷、 脱硫、 去除细小夹杂物的添加剂及其制法和应角 技术领域
本发明涉及一种各种微合金钢以及特殊钢的炉外精炼工艺， 特别是一种 用于钢水炉外精炼脱磷、 脱硫、 去除细小夹杂物的添加剂及其制法和应用， 是各种微合金钢或特殊钢精炼中脱磷、 脱硫及去除细小夹杂物首选的添加剂 与应用工艺。
背景技术
众所周知， 磷和硫对大多数钢种来讲是有害的， 钢水中硫含量的减少将 有助于提高钢的抗层状断裂， 磷可降低钢的冲击韧性， 尤其是低温冲击韧性， 磷的枝晶偏析使板材产生带状组织， 造成钢板各相异性。 夹杂物对钢材的危 害主要与夹杂物的数量和尺寸有关。 对夹杂物进行质量控制， 首要的是控制 夹杂物的数量和尺寸。 由于钢种不同和冶炼成本限制， 对夹杂物的要求也不 尽相同， 对普通钢， 总氧 50ppm、夹杂物大小在 50μιη以下， 通常对钢材性能 不构成严重的质量问题。 然而， 对 IF钢、 硅钢、 帘线钢和管线钢等， 这个指 标可能根本达不到要求， 例如， 钢帘线要求 A1203夹杂小于 10〜15μπι， 才能 满足拉丝过程中 20万米无断头的要求。
近年来， 由于钢包精炼技术及连铸技术的进步， 钢中磷、 硫含量得到降 低， 非金属夹杂物的数量也明显减少。 但是， 由于钢材的用途和使用条件的 苛刻， 对钢中磷、 硫和夹杂物的要求更加严格。 提高钢铁产品质量、 生产纯 净钢的关键在于控制钢中磷、 硫含量以及夹杂物的数量。 降低钢中磷、 硫含 量， 生产洁净的钢水， 其主要措施之一是降低锰铁熔体的磷含量， 并采用炉 外精炼工艺。 在精炼过程中添加精炼剂。 对钢水进行脱硫、 脱磷， 当前脱硫 采用 CaO-Al203基钢水炉外脱硫剂， 脱磷则采用 CaO-FeO基钢水炉外脱磷精 炼剂。 存在缺陷是： CaO-Al203基钢水炉外脱硫精炼剂只能脱硫， 不能脱磷；
1
确认本 CaO-FeO基钢水炉外脱磷精炼剂不仅脱磷效果不佳，而且在精炼造还原渣后， 钢水严重回磷， 污染了钢水， 影响生产。 钢液中的夹杂物大部分是通过浮力 自然上浮去除的， 可以说这种情况在整个冶金过程中一直在进行。 但是， 炼 钢是大规模连续生产， 仅靠自然上浮效率很低， 无法满足生产要求， 因此常 常采用专门的手段， 例如炉外精炼、 过滤等， 强化夹杂物的去除。 吹氩搅拌 是钢包重要的精炼手段之一， 底吹氩可以均匀钢液的成分和温度，最重要的功 能是促进钢液中夹杂物的去除。
虽然上述方法能在一定程度上降低钢液中磷、 硫含量， 去除夹杂物， 但 是却不能对钢中磷、 硫以及细小夹杂物同时进行有效的控制。
发明内容
本发明是针对上述现有技术中存在的问题提供一种能稳定控制钢液中 磷、 硫含量以及夹杂物的尺寸和数量分布的添加剂， 效果明显、 稳定、 确保 和提高精炼钢的质量， 降低冶炼成本， 并制备工艺简单， 多种剂型利于使用、 操作、 运输和储存。
本发明的另一个目的是所述的添加剂在钢液炉外精炼中的应用。
为了解决上述技术问题， 本发明是这样实现的： 用于炉外精炼脱磷、 脱 硫、 去除细小夹杂物的添加剂， 它是由球芯和外壳构成的复合球体， 所述的 球芯主要由低熔点预熔渣粉剂、 碳酸钙、 碳酸镁或碳酸钙与碳酸镁的混合物 构成， 所述的外壳主要由氧化钙或氧化镁的一种或两种的混合物构成。
所述的球芯由下述原料按重量百分比制备而成：
低熔点预熔渣粉剂 1 %〜70%
碳酸钙、 碳酸镁或碳酸钙与碳酸镁的混合物 1%〜60%
氟化钙 0〜40%
粘结剂 0〜20%
所述的球芯由下述原料按重量百分比制备而成： 低熔点预熔渣粉剂 10%〜50% 碳酸钙、 碳酸镁或碳酸钙与碳酸镁的混合物 10%〜45%
氟化钙 5%〜30%
粘结剂 50/0〜15%
所述的低熔点预熔渣粉剂由如下原料按重量百分比经制备而成： CaO 10%〜70%, A1203 15%〜50%， Si02 0〜10%， MgO 0〜10%， CaF2 0〜30 % , 其熔点在 1100° (：〜 1550°C。
所述的外壳还包括 0〜20%的粘结剂。
用于炉外精炼脱磷、 脱硫、 去除细小夹杂物的添加剂， 主要由低熔点预 熔渣粉剂、 碳酸钙、 碳酸镁或碳酸钙与碳酸镁的混合物和氧化钙或氧化镁的 一种或两种的混合物构成的粉剂。
所述的添加剂由下述原料按重量百分比制备而成：
低熔点预熔渣粉剂 1%〜70%
碳酸钙、 碳酸镁或碳酸钙与碳酸镁的混合物 10/0〜60%
氧化钙或氧化镁或氧化鈣与氧化镁的混合物 10ο/ο〜98% 氟化钙 0〜40%
粘结剂 0〜20%
所述的添加剂， 其特征在于主要由下述原料按重： ：百分比制备而成: 低熔点预熔渣粉剂 10%〜50% 碳酸钙、 碳酸镁或碳酸钙与碳酸镁的混合物 10%〜45% 氧化钙或氧化镁或氧化钙与氧化镁的混合物 30ο/ο〜70% 氟化钙 5%〜30%
粘结剂 5%〜15%
所述原料的粒度在 lnm〜3.5mm， 其中氧化钙、 氧化镁的活度 ^SOOmL 所述的添加剂还包括包芯线剂型。 所述的粘结剂为粘土、 普通水泥、 膨润土、 水玻璃中任意一种或两种以 上的混合物。
所述添加剂的工艺方法， 包括以下步骤：
1 )、 制备球芯：
(a)、混料：按配方配比取芯部所需的原料粉剂，其粒径为 Inn！〜 3.5mm， 将上述的粉料与粘结剂放入混料器中进行充分搅拌混合， 混料时间为 1 h〜3h 备用。 （b)、 烘干： 将上述混合后的粉料在烘干机中进行烘干处理， 烘干温度 为 80°C〜150°C， 时间为 21！〜 8 h。 （c)、 制球芯： 将上述烘干处理后的粉料通 过制球设备制球芯， 并使球芯的直径为 0.05mn！〜 40mm。
2)、 制备复合球体：
(d)、 外壳混料： 按配比将外壳所需的原料在混料器中进行充分混合， 氧化钙、氧化镁的活度 200ml， 混料时间为 1 1！〜 3h备用。 （e)、 复合： 将上 述已制好的球芯与外壳原料通过滚动方法在制球设备上进行复合制球， 其中 制好的复合球体尺寸为 20〜80mm; 制好的复合球丸的直径控制在 0.25〜 20mm。（f)、整体烘干： 将上述步骤制好的复合球体、球丸在烘干机中进行烘 干处理， 烘干温度为 60° (：〜 200 °C， 时间为 101！〜 24h， 成品包装。
所述添加剂的制备方法， 包括以下步骤：
①混料配制粉剂： 按配方配比取其粒度为 Inn！〜 3.5mm的低熔点预熔渣 粉、 氟化钙、 碳酸钙、 碳酸镁或碳酸钙与碳酸镁的混合物、 氧化钙、 氧化镁 或氧化钙与氧化镁的混合物和粘合剂入混料器中进行充分搅拌混合， 混料时 间 11！〜 8 ho
②烘干处理： 将上述配制的粉剂在 80°C〜200°C烘干设备中烘干， 时间为 21！〜 24h即为成品粉剂。
所述添加剂的制备方法， 还包括下述步骤：
③制线： 以厚度为 2mm〜5 mm的低碳钢带作为包芯线的外皮， 以制备的 成品粉剂为线芯在制线机上，采用单层钢带搭接式制包芯线，包线速度为 8〜 30m/min, 包芯线的粉剂含量在 100〜240g/m即为成品， 包装。
所述的添加剂在炉外精炼过程脱磷、 脱硫及去除细小夹杂物中的应用。 本发明的添加剂在各种微合金钢以及特殊钢的精炼生产过程中， 能同时 脱磷、脱硫及去除细小夹杂物的愿望成为现实，并通过在 LF、RH、VD、CAS-OB 中间包或结晶器中喂入即可稳定控制钢液中磷、 硫以及夹杂物的尺寸数量与 分布， 而且取得理想的效果。
本发明采用碳酸钙、 碳酸镁或碳酸钙与碳酸镁的混合物超细粉料作为微 小气泡的原位生成剂， 碳酸钙、 碳酸镁的分解过程如下：
825V , 、
CaC03→ C02 †+CaO ( 1 )
825 °C
MgC03→ C02 T+MgO (2)
当碳酸钙、 碳酸镁粉料足够细小时， 产生气泡的尺寸与粉料的大小相当。 因此可以在钢水中引入超细气泡（气泡的尺寸在 10〜300 m之间）。气泡的尺 寸越细小， 夹杂物的去除效率越高。 此外， 加入的氧化钙、 氧化镁或氧化钙 与氧化镁的混合物 +低熔点预瑢澄 +氟化钙 +碳酸钙、碳酸镁或碳酸钙与碳酸 镁的混合物的本发明添加剂分解反应后的另一产物氧化镁或氧化钙尺寸细 小，能够在钢液中迅速熔化形成渣滴并与钢液中的 Α1203夹杂物形成低熔点钙 铝酸盐，易于上浮到钢包渣中，从而降低精炼产生的 Α1203夹杂物的数量与尺 寸。
石灰作为脱磷溶剂的固定剂， 以高活性氧化钙形式存在， 高活性氧化钙 快速熔化后， 即与 Ρ205形成 3CaO * P205或者 4CaO ' P205， 可以将磷固定并 排出到渣中。 此外， 以往用石灰作为脱硫剂进行脱硫的处理时， 2CaO+2S= 2CaS+02, 反应产生的氧与钢液内的硅结合， 产生二氧化硅（Si02)， 随着石 灰的加入， 该二氧化硅形成了硅酸二钙， 而硅酸二钙形成固体层包裹在石灰 粉料表面。 结果不利于石灰粉粒的脱硫效果。 喂入细小氧化钙粉料可在较短 的时间充分发生反应从而避免在氧化钙表面形成硅酸二钙， 提高了活性氧化 钙粉料的利用率。
本发明与现有技术相比， 由于配方科学合理当其加入钢水中产生细小气 泡， 与夹杂物的碰撞概率高， 同时细小渣滴具有渣洗功能， 亦能对钢液中的 夹杂物进行有效去除， 并经应用证明， 本发明的添加剂具有多功能， 不仅能 脱磷、 脱硫， 而且还能有效控制钢水中细小夹杂物的数量尺寸与分布， 采用 本发明的添加剂，可将钢中总氧、硫、磷的含量分别控制在 3-15ppm、 5-30ppm、 10-50ppm,夹杂物的当量直径为 0.3-5μιη; 同时，制备工艺简单、灵活、方便， 且剂型多、 利于应用， 可采用喂线、 喷粉、 射丸甚至球体状直接投入的方式 在 LF、 RH、 VD、 CAS-OB、 中间包或结晶器中喂入， 操作方便； 同时明显 提高钢水的纯净度降低冶炼成本。
具体实施方式
下面结合具体实施例对本发明内容进行进一步详细说明， 但本发明的保 护范围不受具体的实施例所限制， 以权利要求书为准。 另外， 以不违背本发 明技术方案的前提下， 对本发明所作的本领域普通技术人员容易实现的任何 改动或改变都将落入本发明的权利要求范围之内。
实施例 1
低熔点预熔渣的制备， 按配方配比取 CaO粉 40kg、 A1203粉 35 kg、 Si02 粉 10 kg、 ^¾0粉101¾ 、 CaF2粉 5 kg放入混料器中迸行均匀混料， 然后在 镁砂坩埚中熔化、 冷却， 后研磨成粒径为 Inn！〜 3.5mm 的粉料， 其熔点在 1100〜1550°C备用；再按配方配比分别取其粒径为 1 nm~3.5mm的低熔点预熔 渣粉 35 kg、 氟化钙粉 5 kg、 氧化钙粉 55 kg、 碳酸钙 5 kg入混料器进行均匀 混料 l〜8h， 其中所述氧化钙的活度 2001111; 制备好的粉料入 80~200°C烘干 设备进行烘干 8 h〜24 h即为成品粉剂； 冷却至室温后进行防潮密封包装 500 kg/袋， 并在 10天内使用。 实施例 2
按配方配比取 CaOlO kg、 Al2O350 kg、 Si025 kg、 MgO 5 kg、 CaF230 kg 制备低熔点预熔渣粉； 取制备好的低熔点预熔渣粉 1 kg、 氟化钙 30 kg、 碳酸 镁 40 kg、 氧化镁 29 kg。 其制备组合粉剂工艺、 烘干处理与实施例 1相同； 在烘干处理后的粉剂以厚度为 2mm〜5 mm的普通低碳钢带作为包芯线的外 皮， 线芯为经过烘干的上述粉剂在制线机上， 采用单层钢带搭接式制包芯线， 包芯线速度为 8〜30m/min， 包芯线的粉剂含量在 100〜240g/m， 装成 1000〜 2000m/卷， 利于使用中控制加入量与加入速度， 包芯线的截面为圆形， 包装 要确保密封良好， 防止潮湿， 并在 20天内使用。
实施例 3
按配方配比取 CaO70 kg、 Al20315 kg、 Si023 kg、 MgO 2 kg、 CaF210 kg 制备低烙点预熔澄粉的方法同实施例 1 ; 取制备好的低熔点预熔渣粉 45 kg, 碳酸钙与碳酸镁的混合粉 30 kg (两者的配比并不严格)， 氧化钙与氧化俵的 混合物 10 kg、 粘结剂 15 kg; 按上述配比将球芯所需的固体原料进行破碎碾 压， 同时还采用气流微粉磨研磨， 达到粒径为 80ηπ！〜 3mm， 再将上述球芯粉 料放入混料器中进行充分搅拌混合，混料时间为 l〜3h。将混合后的原料在烘 干设备中进行烘干处理， 烘干温度为 100〜140°C， 时间为 2〜4 h。将上述烘干 处理后的粉料采用挤压方法在压球机上制球芯， 球芯大小的控制通过筛分进 行确定， 得到球芯的直径为 0.05〜40mm。 按上述配比取外壳所需的粉料在混 料器中进行充分混合， 氧化钙的活度 200ml， 混料时间为 l〜3h。 再将已制 好的球芯与外壳原料通过滚动方法在圆盘造球机上进行复合制球， 通过筛分 对球体大小进行控制确定，制好的复合球体尺寸为 20〜80mm，最后将复合球 体在 90〜160°C烘干， 烘干时间 10〜15h， 冷却至室温分别包装 10 kg〜30kg/ 袋， 并在 20天内使用。
实施例 4 按配方配比取 CaO50 kg、 Al2O340 kg、 Si025 kg、 MgO 5 kg, 制备低熔点 预熔渣粉的方法同实施例 1；取制备好的低熔点预熔渣粉 60 kg、氟化钙 10 kg、 碳酸钙 1 kg、氧化镁 25 kg、粘结剂 4 kg与实施例 1相同方法制成粉剂； 按上 述配比将球芯所需的固体原料进行破碎碾压， 同时还采用气流微粉磨研磨， 达到粒径为 lnm〜： L.5mm， 再将上述球芯粉料放入混料器中进行充分搅拌混 合， 混料时间为 l〜3h。 将上述混合后的原料再在烘干设备中进行烘干处理， 烘干温度为 80〜110°C， 时间为 2〜6h。 将上述烘干处理后的原料采用挤压方 法在压球机上制球芯， 球芯大小的控制通过筛分进行确定， 得到球芯的直径 为 0.05〜40mm。 按上述配比取外壳所需的粉料在混料器中进行充分混合， 氧 化钙的活度 200ml， 混料时间为 l〜3h。 将己制好的球芯与外壳原料通过滚 动方法在圆盘造粒机上进行复合制丸， 通过筛分对球丸大小进行控制确定， 制好的复合球丸尺寸为 0.25〜20mm， 最后将其在 60〜120°C烘干， 烘干时间 10〜18h， 冷却至室温将其分别包装 10〜30kg/袋， 并在 20天内使用。
实施例 5
按配方配比取 CaO50 kg、 Al2O330 kg、 CaF220 kg, 制备低熔点预熔渣粉 的方法同实施例 1 ; 取制备好的低熔点预熔渣粉 3 kg、 氟化钙 2 kg、 碳酸钙 10 kg、 氧化镁 85 kg与实施例 1相同方法制粉、 烘干后， 以厚度为 2mm的低 碳钢带作为包芯线的外皮， 线芯为经过烘干的上述粉剂在制线机上， 用实施 例 2相同方法制包芯线， 包装成 1000m/卷， 其截面为方形， 在 20天内使用。 实施例 6
按配方配比取 Ca025 kg、 Al20345 kg、 Si028 kg、 MgO 8 kg、 CaF214 kg 制备低熔点预熔澄粉备用； 取制备好的低熔点预熔渣粉 2 kg、 氟化钙 18 kg、 碳酸镁 55 kg、 氧化钙 15 kg、 粘结剂 10 kg, 除所用原料的粒度在 0.01mm〜 0.8mm外与实施例 1相同方法制成粉剂； 釆用与实施例 4相同方法制复合制 丸， 通过筛分对球丸大小进行控制确定， 其直径控制在 5mm〜15mm， 在 90 °C〜120°C烘干 10〜15h冷却至室温包装 500kg/袋， 并在 20天内使用。 实施例 7
取实施例 6备用的低熔点预熔渣粉 20 kg、用气流微粉磨加工成粒度在 1〜 50nm的碳酸镁粉 20 kg、其余原料的粒度在 0.4mm〜3.4mni之间，氧化钙 40 kg、 粘结剂 20 kg进行均匀混料，制成粉剂，采用与实施例 3相同方法制复合球体， 通过筛分对球体大小进行控制确定，其直径控制在 30mm ~60mm;在 100°C〜 200°C烘干设备中烘干 10h〜24h,冷却至室温包装成 1000kg/袋，在 20天内使 用。
实施例 1至 7中所述的粘结剂为粘土、 普通水泥、 膨润土、 水玻璃中一 种或任意两种或两种以上的混合。
下面为本发明的添加剂在各种微合金钢及特殊钢的炉外精炼脱磷、脱硫及 去除细小夹杂物中的应用。
应用实施例 1
采用喷粉工艺， 在 LF、 RH或 CAS-OB精炼后期喷入粉剂， 输送气压控制 在 0.01〜1.5MPa,本发明添加剂加入量为 0.5〜5kg/t，其粉剂的输送量在 0.01〜
3 kg/s。 当添加剂加入钢水后由于碳酸钙、 碳酸镁粉料足够细小， 从而产生弥 散细小的气泡， 气泡越小， 夹杂物的去除效率越高， 与此同时添加剂分解另 一产物活性氧化钙的粒度越细小， 就越能在钢液中迅速熔化形成渣滴， 并与 钢液中的 A1203夹杂物形成低熔点钙铝酸盐，易于上浮到钢包渣中，具有渣洗 功能。
应用实施例 2
在转炉出钢运到 LF工位， 测温取样、 调节成分， 当合金化结束后， 将包 芯线从 LF工位喂入包芯线， 喂线过程停止吹氩搅拌， 喂线速度 150〜350m/ min，喂入量在 0.1〜2.4kg/t，喂线后静止 l〜5min进行吹氩轻处理,压力 0.13〜 0.8 1\^¾氩气的流量为50〜120 /11 1， 弱吹氩时间 3〜5min， 吹氩结束后立 即搬出， 连铸采用全程保护浇注。 也可以在 RH下降管一侧喂线， 喂线速度 180〜350m/ min， 喂入量在 0.5〜4.5kg/t， 喂线后 RH循环时间为 3〜10min, 循环结束后立即搬出浇注， 连铸采用全程保护浇注。
沿铸坯内弧 1/4处取样在 500倍显微镜下分析夹杂物形貌和粒度，并采用 定量金相分析夹杂物面积含量 （分析面积为 lOX lOmm), 釆用氮氧仪分析全 氧含量， 采用化学分析的方法测定 S、 P含量分析结果如表 1
表 1 应用实施例与对比例的试验结果
Figure imgf000011_0001
由表 1看出,本发明的添加剂在各种微合金钢以及特殊钢炉外精炼中脱磷、 脱硫与去除杂物的应用中取得令人满意的效果， 为所述钢的精炼质量提升一 个新的高度， 提供一种首选的多功能添加剂， 并有效降低冶炼成本。
应用实施例 3
在 CAS-OB 合金化处理后， 将包芯线喂入钢液， 喂线速度在 200〜 350m/min,喂入量在 0.5〜4.5kg/t。喂线后底吹氩气搅拌，氩气强度为 0.001〜 0.004m3 /rnin-t, 吹氩时间在 l〜10min， 连铸采用全程保护浇注； 或者当钢包 运到 VD工位后立即喂包芯线， 速度在 200〜350m/min， 0.5〜4.5kg/t， VD炉 保护压 67Pa不小于 15分钟， 或预抽加保压时间不小于 25分钟； VD真空处 理期间氩气压力不小于 O.lmpa, 氩气流量 80〜100 Nl /min, 连铸采用全程保 护浇注。 ， 应用实施例 4
直接将包芯线喂入中间包， 喂线位置为长水口下方， 喂线速度在 200〜 350m/min, 喂入量在 l〜3kg/t; 或直接将包芯线喂入结晶器中， 其喂线速度 与加入量与从中间包喂入的相同。
应用实施例 5
采用射丸设备在 LF、 RH、 VD、 CAS-OB、 中间包或结晶器将添加剂的丸 剂喂入钢液， 以氩气为载体，气压控制在 0.1〜1.0 MPa,射入量为 0.5〜5kg/t。 连铸采用全程保护浇注。
应用实施例 6
(1)调节 RH下降管与下料管的位置， 使之处于下料管的异侧；
(2)钢包运到 RH工位后，测温取样，冶炼过程钢水实际温度高于正常生产 温度 5〜10°C，调节成份，当合金化结束后，并且当真空室真空度在 80〜300Pa 时， 由合金料仓投入复合球体状添加剂， 加入量为 0.8〜2.5kg/t， 单次加入量 在 50〜130kg， 两次加入间隔在 l〜5min; 球体加入后循环 l〜10min; 连铸采 用全程保护浇注。 该球体状添加剂抗压强度 5〜35MPa， 热稳定性高， 1600°C 延时爆裂时间在 10s以上。
沿铸坯内弧 1/4处取样在 500倍显微镜下分析夹杂物形貌和粒度，并釆用 定量金相分析夹杂物面积含量（分析面积为 10X 10mm)， 釆用氮氧仪分析全 氧含量， 采用化学分析的方法测定 S、 P含量分析结果如表 2所示。
表 2应用实施例与对比例的试验结果
Figure imgf000012_0001

Claims

权 利 要 求
1、 用于炉外精炼脱磷、 脱硫、 去除细小夹杂物的添加剂， 其特征在于它 是由球芯和外壳构成的复合球体， 所述的球芯主要由低熔点预熔渣粉剂、 碳 酸钙、 碳酸镁或碳酸钙与碳酸镁的混合物构成， 所述的外壳主要由氧化钙或 氧化镁的一种或两种的混合物构成。
2、 根据权利要求 1所述的添加剂， 其特征在于所述的球芯由下述原料按 重量百分比制备而成- 低熔点预熔渣粉剂 1%〜70%
碳酸钙、 碳酸镁或碳酸钙与碳酸镁的混合物 1%〜60%
氟化钙 0〜40%
粘结剂 0〜20%
3、 根据权利要求 1所述的添加剂， 其特征在于所述的球芯由下述原料按 重量百分比制备而成：
低熔点预熔渣粉剂 10%〜50% 碳酸钙、 碳酸镁或碳酸钙与碳酸镁的混合物 10ο/ο〜45%
氟化钙 5%〜30%
粘结剂 5%〜15%
4、 根据权利要求 1所述的添加剂， 其特征在于所述的低熔点预熔澄粉剂 由如下原料按重量百分比经制备而成： CaO 10%〜70%， A1203 15%〜50%， Si02 0〜； 10%， MgO 0〜10%, CaF2 0〜30%， 其熔点在 1100°C〜1550°C。
5、 根据权利要求 1所述的添加剂， 其特征在于所述的外壳还包括 0〜20 %的粘结剂。
6、 用于炉外精炼脱磷、 脱硫、 去除细小夹杂物的添加剂， 其特征在于主 要由低熔点预熔渣粉剂、 碳酸钙、 碳酸镁或碳酸钙与碳酸镁的混合物和氧化 钙或氧化镁的一种或两种的混合物构成的粉剂。
7、 根据权利要求 6所述的添加剂， 其特征在于由下述原料按重量百分 比制备而成：
低熔点预熔渣粉剂 1%〜70%
碳酸钙、 碳酸镁或碳酸钙与碳酸镁的混合物 1%〜60%
氧化钙或氧化镁或氧化钙与氧化镁的混合物 10%〜98%
氟化钙 0〜概
粘结剂 0〜20%
8、 根据权利要求 6所述的添加剂， 其特征在于主要由下述原料按重 百分比制备而成：
低熔点预熔渣粉剂 10%〜50%
碳酸钙、 碳酸镁或碳酸钙与碳酸镁的混合物 10%〜45%
氧化钙或氧化镁或氧化钙与氧化镁的混合物 30%〜70%
氟化钙 5%〜30%
粘结剂
Figure imgf000014_0001
9、 根据权利要求 6所述的添加剂， 其特征是所述原料的粒度在 Inn！〜 3.5mm, 其中氧化钙、 氧化镁的活度 200ml。
10、 根据权利要求 6所述的添加剂， 其特征在于所述的添加剂还包括包 芯线剂型。
11、 根据权利要求 7或 8所述的添加剂， 其特征在于所述的粘结剂为粘 土、 普通水泥、 膨润土、 水玻璃中任意一种或两种以上的混合物。
12、 制备权利要求 1所述添加剂的工艺方法， 其特征在于包括以下步骤: 1 )、 制备球芯：
(a)、 混料： 按配方配比取芯部所需原料粉剂， 其粒径为 lnm〜3.5mm， 将上述的粉料与粘结剂放入混料器中进行充分搅拌混合， 混料时间为 1！！〜 3h 备用。 (b)、 烘干： 将上述混合后的粉料在烘干机中进行烘干处理， 烘干温度 为 80°C〜150°C， 时间为 2 h〜8 h。
(c)、 制球芯： 将上述烘干处理后的粉料通过制球设备制球芯， 并使球 芯的直径为 0.05mm〜40mm。
2)、 制备复合球体：
(d)、 外壳混料： 按配比将外壳所需的原料在混料器中进行充分混合， 氧化钙、 氧化镁的活度 200ml, 混料时间为 l h〜3h备用。
(e)、 复合： 将上述已制好的球芯与外壳原料通过滚动方法在制球设备 上进行复合制球，其中制好的复合球体尺寸为 20〜80mm;制好的复合球丸的 直径控制在 0.25〜20mm。
(f)、整体烘干： 将上述步骤制好的复合球体、球丸在烘干机中进行烘干 处理， 烘干温度为 60°C〜200°C， 时间为 101！〜 24h， 成品包装。
13、 制备权利要求 6所述添加剂的工艺方法， 其特征在于包括以下步骤:
①混料配制粉剂： 按配方配比取其粒度为 lnm〜3.5mm的低熔点预熔渣 粉、 氟化钙、 碳酸钙、 碳酸镁或碳酸钙与碳酸镁的混合物、 氧化钙、 氧化镁 或氧化钙与氧化镁的混合物和粘合剂入混料器中进行充分搅拌混合， 混料时 间 11！〜 8 ho
②烘干处理： 将上述配制的粉剂在 80°C〜200°C烘干设备中烘干， 时间为 21！〜 24h即为成品粉剂， 包装。
14、 根据权利要求 13所述的工艺方法， 其特征在于还包括下述步骤-
③制线： 以厚度为 2mm〜5 mm的低碳钢带作为包芯线的外皮， 以制备的 成品粉剂为线芯在制线机上，釆用单层钢带搭接式制包芯线，包线速度为 8〜 30m/min， 包芯线的粉剂含量在 100〜240g/m即为成品， 包装。
15、 所述的添加剂在炉外精炼过程脱磷、 脱硫及去除细小夹杂物中的应 用。
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CN103146877A (zh) * 2013-02-04 2013-06-12 安徽省繁昌县皖南阀门铸造有限公司 一种含有竹炭的炼钢精炼剂及其制备方法
CN103146884A (zh) * 2013-02-04 2013-06-12 安徽省繁昌县皖南阀门铸造有限公司 一种镁铝硅钢水炉外精炼剂及其制备方法
CN103184314A (zh) * 2013-03-12 2013-07-03 邢台钢铁有限责任公司 一种aod炉进行铁水脱磷的冶炼方法
CN113025782A (zh) * 2021-02-07 2021-06-25 首钢集团有限公司 一种快速脱硫的方法
CN113444853A (zh) * 2021-06-25 2021-09-28 中钢设备有限公司 一种细颗粒Mg-CaO复合脱硫剂及其制备方法、一种铁水预脱硫的方法
CN113862427A (zh) * 2021-09-26 2021-12-31 张家港荣盛特钢有限公司 一种精炼渣及其制备方法和应用
CN114574661A (zh) * 2022-03-17 2022-06-03 佛山市南海创利有色金属制品有限公司 一种新型环保精炼剂及其制备方法
CN114672718A (zh) * 2022-04-13 2022-06-28 张家港扬子江冷轧板有限公司 高牌号硅钢的冶炼方法
CN114672718B (zh) * 2022-04-13 2023-07-07 张家港扬子江冷轧板有限公司 高牌号硅钢的冶炼方法
CN115198055A (zh) * 2022-06-16 2022-10-18 莱芜钢铁集团银山型钢有限公司 一种具有吹氩功能的连铸中间包湍流控制器及其制备方法
CN115198055B (zh) * 2022-06-16 2023-06-09 莱芜钢铁集团银山型钢有限公司 一种具有吹氩功能的连铸中间包湍流控制器及其制备方法

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