CN102876848A - Method for producing low sulphur steel through carrying out CAS-OB refining on premelting calcium aluminate - Google Patents
Method for producing low sulphur steel through carrying out CAS-OB refining on premelting calcium aluminate Download PDFInfo
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Abstract
The invention provides a method for producing low sulphur steel through carrying out CAS-OB (Composition Adjustment by Sealed Argon Bubbling-Oxygen Bubbling) molten steel ladle refining on premelting calcium aluminate. The method mainly comprises the following steps: converter tapping, deep desulfurization in a CAS-OB refining furnace (argon stirring is carried out on molten steel during the whole process of refining desulfurization), drossing, refining, alloying treatment and continuous casting. Deep desulfurization is carried out by the method, so that the desulfurization rate can reach more than 85%, the sulfur content in the molten steel can be controlled below 0.002% stably, and the desulfurization efficiency is high and stable. Compared with the prior art, the method is simple to operate and stable in desulfurization effect, and does not influence the production rhythm. A used desulfurizer is aluminum-calcium premelting refining slag, is subjected to high-temperature melting treatment during the manufacturing process, has the characteristics of uniform compositions, low sulphur and low melting point, can achieve slugging quickly to desulfurize quickly, and reduces the environmental pollution.
Description
Technical field
The invention belongs to metallurgical technology field, be used in the external refining process, the application preliminary melting type calcium aluminate removes the sulphur in the steel, especially using preliminary melting type calcium aluminate is the molten steel treatment unit of sealed argon-blowing stirring and adjusting composition in the meaning of CAS-OB[CAS (Composition Adjustment by Sealed Argon Bubbling), and OB means can heating by O2 blowing] refining furnace carries out producing in the molten steel furnace external refining process method of low-sulfur steel.
Background technology
Sulphur is harmful element (except the free-cutting steel) in most of steel grades, the ductility and the toughness that are mingled with meeting reduction steel of steel medium sulphide content.Therefore, reduce sulphur content in the steel to the defective that reduces steel, improve steel mechanical property most important.So a lot of steel grades all require to fall sulphur content more low better.By literature search, " E.T.Turkdogan Fundamentals of Steelmaking " mentions the Japanese monarch Tianjin V-KIP of Steel Plant (Vacuum-Kimizu Injeet Procass, be vacuum-monarch Tianjin inject process LADLE REFINING PROCESS AND) sulphur can be taken off to 0.0002%～0.0005%, in all refining units, it can be maximum that V-KIP stirs, sweetening power is the strongest, and still, domestic do not have this kind equipment.Chinese patent 200610047101.X is a kind of deep desulfurizer for refining ultra-low-carbon steel and manufacture method, changes that to mention its sweetening effectiveness in the document better, but calculates the oxide compound in the basic inadequate reduced steel slag of its aluminium content by theoretic material balance.Therefore, can not finish dark desulfurization; And its sulfur removal technology is too complicated, and carry out reinforced dividing for 5～15 times, also will carry out temperature detection at every turn, and technological operation becomes difficult point, and repeatedly thermometric has also improved cost indirectly simultaneously.In addition, in this sweetening agent, also contain 1%～3% fluorite, at present, because it not only can affect the work-ing life of body of heater or ladle lining refractories, but also can be to environment, country has prohibited at steelmaking process and has used fluorite.Therefore, for the high-quality low-sulfur steel, need urgently to develop a kind of efficient sweetening agent and a kind of effective sulfur removal technology or method.
Be rich in the calcareous pre-melted refining slag of aluminium of aluminum oxide and calcium oxide, fusing point is low, molten speed is fast, sulfur capacity is high, forms stable performance through high-temperature fusion, never degenerate, do not absorb water, not efflorescence, low fluorine, molten steel is being carried out not only can promote molten steel desulfurizing in the refining process, refractory consumption rate is polluted, reduces in also favourable environmental protection, minimizing.Thereby it is very suitable for producing the high-quality low-sulfur steel.
Summary of the invention
The present invention be directed to that above-mentioned problems of the prior art propose, its objective is provides a kind of application preliminary melting type calcium aluminate to carry out the molten steel furnace external refining desulfurization at the CAS-OB refining furnace, sulphur content in the molten steel can be stablized and be controlled at below 0.002%, successful, stable, and guarantee and improve the quality of refining steel, reduce the processing method that the outside-stove refining dephosphorization of smelting cost is produced low-sulfur steel.
In order to reach the foregoing invention purpose, technical scheme of the present invention is as follows, and the method that the application preliminary melting type calcium aluminate carries out CAS-OB molten steel furnace external refining production low-sulfur steel mainly may further comprise the steps:
(1) converter tapping: after converter smelting finished, tapping temperature was controlled at 1650 ℃～1750 ℃, and adopted pushing off the slag to process in the tapping process, carried out the deoxidation operation, then carried out pre-alloyed processing;
(2) the dark desulfurization of CAS-OB refining furnace: ladle is transported to CAS-OB refining station, at first opens the argon gas valve and carries out the Argon stirring, then adds preliminary melting type calcium aluminate in ladle, all will carry out Argon to molten steel in the whole refining desulfuration process and stir;
(3) skim: refining desulfuration is transported to the station of skimming with ladle after finishing, and the slag that utilizes slag removal machine that rear molten steel surface is processed in desulfurization removes, and then adds ladle covering agent;
(4) refining, Alloying Treatment: at refining furnace molten steel is carried out temperature adjustment processing and stir process, liquid steel temperature should be controlled at 1570 ℃～1600 ℃ after processing finished; According to different steel grade smelting requirements, add alloy to molten steel again and carry out the alloying operation, also to carry out the argon gas stirring operation in refining and the alloying process;
(5) continuous casting: adopt the whole process protection cast.
It can be silicon deoxidation, aluminium deoxidation or other conventional deoxidation modes that described deoxidation operation requires according to steel grade.
Wherein, described pushing off the slag processing is to adopt any one mode in floating plug, slag-blocking ball or the slag stop cone to realize.
The adding mode of described preliminary melting type calcium aluminate can be that one or many adds molten steel, and the adding mode can be by bin blanking or artificial the input.
Described preliminary melting type calcium aluminate consumption is controlled at 3～20Kg/ ton steel, and granularity is controlled at 0.1mm～100mm.
Its main image of described preliminary melting type calcium aluminate consists of 12CaO7Al
2O
3, 3CaO5Al
2O
3One or more mixture, and other inevitable impurity.
Described Argon in the CAS-OB refining process is processed, and the flow control of argon gas is at 10～500NL/min (standard Liter Per Minute), and the treatment time is controlled at 3～20min.
Described skimming carried out at the station of skimming, and adopts any one equipment in vacuum dreg-sucking machine or the mechanical slag removal machine to realize.
The add-on of described ladle covering agent is controlled at 1～10Kg/ ton steel.
Argon gas in described refining, the Alloying Treatment process stirs flow at 1～100NL/min.
In addition, it is worth mentioning that: the preparation method of the sweetening agent preliminary melting type calcium aluminate among the present invention mainly may further comprise the steps:
The first step: prepare raw material, raw material comprises the material that is rich in calcium oxide and the material that is rich in aluminum oxide;
Second step: the raw material of preparing in the first step is made respectively powder;
The 3rd step: mix, the powder for preparing in the second step is mixed by a certain percentage;
The 4th step: melting, the powder that mixes is added in the high temperature kiln, carry out melting 1450～1600 ℃ of temperature;
The 5th step: come out of the stove post crystallization cooling of melting;
The 6th step: broken moulding, through fragmentation, make and be rich in CaO and Al
2O
3, granularity is the calcareous pre-melted refining slag of block low melting point aluminium of 0.1～100mm (being preferably 70mm).
Wherein, the various trade wastes such as carbide slag, calcium lime powder, paper white sludge, calcium powder that comprise the raw mineral materialss such as calcite, Wingdale, rhombspar and be rich in calcium oxide of the material that is rich in calcium oxide in the raw material.The material that is rich in aluminum oxide in the raw material comprises the trade wastes such as the aluminium ash that is rich in aluminum oxide that produces in the raw mineral materialss such as bauxitic clay and the Industrial processes, aluminium slag.Trade waste in the above-mentioned materials is its chief component, and mineral material is its less important integral part.
The composition range of the calcareous pre-melted desulfurizing agent product of the steelmaking aluminum for preparing at last, is: CaO 40～60%, Al
2O
340～60%, SiO
2≤ 8%, F-≤2%, content of impurities≤5%.
Use method of the present invention to carry out dark desulfurization, its desulfurization degree can reach more than 85%, can make that the element sulphur stable content is controlled at below 0.002% in the steel.Compared with prior art, simple to operate, sweetening effectiveness is stablized, and does not affect rhythm of production.Employed sweetening agent is the calcareous pre-melted refining slag of aluminium, has adopted the high-temperature fusion processing in its manufacturing processed, has homogeneous chemical composition, low fluorine, low-melting characteristics, can realize Fast Slag Melting, reaches the purpose of desulfurization rapidly, and has reduced the pollution to environment.
Embodiment
Below, describe the preferred embodiments of the present invention in detail.Need to prove before this, employed term or word can not limited interpretation be the implication in common implication or the dictionary in this specification and claims book, and should be based in order to illustrate that in the best way principle that its invention contriver can suitably define the concept of term is interpreted as meeting implication and the concept of the technology of the present invention thought.Thereupon, the structure that represents among the embodiment that this specification sheets is put down in writing is one of most preferred embodiment of the present invention, can not represent technological thought of the present invention fully, therefore should be understood that to have for the present invention various equivalents and the variation that can replace.
The below illustrates method of the present invention and produce an effect thereof with several specific embodiments.
Embodiment 1:
After converter smelting finished, tapping temperature was controlled at about 1660 ℃, and adopted pushing off the slag to process in the tapping process, adds reductor (ferrosilicon) molten steel is carried out deoxidation treatment; After having gone out steel ladle is transported to CAS-OB refining station, molten steel is carried out Argon to be stirred, the flow control of argon gas is at 150NL/min, by feed bin is disposable preliminary melting type calcium aluminate is added molten steel, the preliminary melting type calcium aluminate consumption is controlled at 5Kg/ ton steel, and granularity is controlled at 0.1mm～100mm, and the refining treatment time is controlled at 15～20min, refining treatment finishes to stop argon gas and stirs, and ladle is left CAS-OB refining station; Ladle is transported to the station of skimming, and the slag that utilizes slag removal machine that rear molten steel surface is processed in desulfurization removes, and then adds the ladle covering agent of 3Kg/ ton steel; Again ladle is transported to refining furnace molten steel is carried out temperature adjustment, refining treatment, liquid steel temperature should be controlled at 1570 ℃～1600 ℃; Then carry out refining treatment, add a small amount of control oxygen agent (metallic aluminium) to molten steel again, add alloy to molten steel again and carry out the alloying operation; All will carry out the Argon stir process in whole temperature adjustment, refining and the alloying process, argon flow amount is 100NL/min; Continuous casting adopts the whole process protection cast.
Embodiment 2:
After converter smelting finished, tapping temperature was controlled at about 1680 ℃, and adopted pushing off the slag to process in the tapping process, adds reductor (ferrosilicon) molten steel is carried out deoxidation treatment; After having gone out steel ladle is transported to CAS-OB refining station, molten steel is carried out Argon to be stirred, the flow control of argon gas is at 200NL/min, by feed bin is disposable preliminary melting type calcium aluminate is added molten steel, the preliminary melting type calcium aluminate consumption is controlled at 8Kg/ ton steel, and granularity is controlled at 0.1mm～100mm, and the refining treatment time is controlled at 12～15min, refining treatment finishes to stop argon gas and stirs, and ladle is left CAS-OB refining station; Ladle is transported to the station of skimming, and the slag that utilizes slag removal machine that rear molten steel surface is processed in desulfurization removes, and then adds the ladle covering agent of 4Kg/ ton steel; Again ladle is transported to refining furnace molten steel is carried out the temperature adjustment processing, liquid steel temperature should be controlled at 1570 ℃～1600 ℃; Add a small amount of control oxygen agent (metallic aluminium) to molten steel again, then add alloy to molten steel and carry out the alloying operation; All will carry out the Argon stir process in whole refining and the alloying process, argon flow amount is 80NL/min; Continuous casting adopts the whole process protection cast.
Embodiment 3:
After converter smelting finished, tapping temperature was controlled at about 1710 ℃, and adopted pushing off the slag to process in the tapping process, adds reductor (aluminium ferromanganese) molten steel is carried out deoxidation treatment; After having gone out steel ladle is transported to CAS-OB refining station, molten steel is carried out Argon to be stirred, the flow control of argon gas is at 300NL/min, by feed bin is disposable preliminary melting type calcium aluminate is added molten steel, the preliminary melting type calcium aluminate consumption is controlled at 10Kg/ ton steel, and granularity is controlled at 0.1mm～100mm, and the refining treatment time is controlled at 8～10min, refining treatment finishes to stop argon gas and stirs, and ladle is left CAS-OB refining station; Ladle is transported to the station of skimming, and the slag that utilizes slag removal machine that rear molten steel surface is processed in desulfurization removes, and then adds the ladle covering agent of 5Kg/ ton steel; Again ladle is transported to refining furnace molten steel is carried out the temperature adjustment processing, liquid steel temperature should be controlled at 1570 ℃～1600 ℃; Add a small amount of control oxygen agent (metallic aluminium) to molten steel again, then add alloy to molten steel and carry out the alloying operation; All will carry out the Argon stir process in whole temperature adjustment, deoxidation, refining and the alloying process, argon flow amount is 50NL/min; Continuous casting adopts the whole process protection cast.
Embodiment 4:
After converter smelting finished, tapping temperature was controlled at about 1740 ℃, and adopted pushing off the slag to process in the tapping process, adds reductor (aluminium ferromanganese) molten steel is carried out deoxidation treatment; After having gone out steel ladle is transported to CAS-OB refining station, molten steel is carried out Argon to be stirred, the flow control of argon gas is at 350NL/min, at twice preliminary melting type calcium aluminate is added molten steel by feed bin, the processing initial stage adds half preliminary melting type calcium aluminate, refining treatment proceeds to a half and adds second half preliminary melting type calcium aluminate again, the total consumption of preliminary melting type calcium aluminate is controlled at 11Kg/ ton steel, granularity is controlled at 0.1mm～100mm, the refining treatment time is controlled at 5～8min, refining treatment finishes to stop argon gas and stirs, and ladle is left CAS-OB refining station; Ladle is transported to the station of skimming, and the slag that utilizes slag removal machine that rear molten steel surface is processed in desulfurization removes, and then adds the ladle covering agent of 7Kg/ ton steel; Again ladle is transported to refining furnace molten steel is carried out the temperature adjustment processing, liquid steel temperature should be controlled at 1570 ℃～1600 ℃; Add a small amount of control oxygen agent (metallic aluminium) to molten steel again, then add alloy to molten steel and carry out the alloying operation; All will carry out the Argon stir process in whole temperature adjustment, refining and the alloying process, argon flow amount is 30NL/min; Continuous casting adopts the whole process protection cast.
Embodiment 5:
After converter smelting finished, tapping temperature was controlled at about 1720 ℃, and adopted pushing off the slag to process in the tapping process, adds reductor (ferrosilicon) molten steel is carried out deoxidation treatment; After having gone out steel ladle is transported to CAS-OB refining station, molten steel is carried out Argon to be stirred, the flow control of argon gas is at 450NL/min, at twice preliminary melting type calcium aluminate is added molten steel by feed bin, the processing initial stage adds half preliminary melting type calcium aluminate, refining treatment proceeds to a half and adds second half preliminary melting type calcium aluminate again, the total consumption of preliminary melting type calcium aluminate is controlled at 18Kg/ ton steel, granularity is controlled at 0.1mm～100mm, the refining treatment time is controlled at 3～5min, refining treatment finishes to stop argon gas and stirs, and ladle is left CAS-OB refining station; Ladle is transported to the station of skimming, and the slag that utilizes slag removal machine that rear molten steel surface is processed in desulfurization removes, and then adds the ladle covering agent of 8Kg/ ton steel; Again ladle is transported to refining furnace molten steel is carried out the temperature adjustment processing, liquid steel temperature should be controlled at 1570 ℃～1600 ℃; Add a small amount of control oxygen agent (metallic aluminium) to molten steel again, then add alloy to molten steel and carry out the alloying operation; All will carry out the Argon stir process in whole temperature adjustment, refining and the alloying process, argon flow amount is 20NL/min; Continuous casting adopts the whole process protection cast.
Above embodiment 1～5th makes steel at 100 tons of converters, 100 tons of CAS-OB refining furnaces and 100 tons of LF refining furnaces, and its dark sweetening effectiveness sees Table 1.
Table 1 is used preliminary melting type calcium aluminate and is carried out the dark desulfurization result of external refining
| Embodiment | The converter tapping sulphur content, % | Finished product sulphur, % | Desulfurization degree, % |
| Embodiment 1 | 0.015 | 0.0014 | 90.6 |
| Embodiment 2 | 0.017 | 0.0018 | 89.4 |
| Embodiment 3 | 0.018 | 0.0007 | 96.1 |
| Embodiment 4 | 0.021 | 0.0013 | 93.8 |
| Embodiment 5 | 0.016 | 0.0015 | 90.6 |
This shows, use the desulfurization degree of the steel that method of the present invention produces high, and technique is clear, equipment is simple, is suitable for industrial production and popularization.
Be described and illustrate with reference to embodiment although it should be noted that the present invention, and in embodiment, provided and use preliminary melting type calcium aluminate and carry out the concrete technology step that the CAS-OB molten steel furnace external refining is produced the method for low-sulfur steel.But and do not mean that the present invention is limited to the embodiment of these descriptions.Those skilled in the art can therefrom derive many different variants, and they all will be covered in the true spirit and scope of claim of the present invention.
Claims (10)
1. use the method that preliminary melting type calcium aluminate carries out CAS-OB molten steel furnace external refining production low-sulfur steel for one kind, it is characterized in that:
The method mainly may further comprise the steps:
(1) converter tapping: after converter smelting finished, tapping temperature was controlled at 1650 ℃～1750 ℃, and adopted pushing off the slag to process in the tapping process, carried out the deoxidation operation, then carried out pre-alloyed processing;
(2) the dark desulfurization of CAS-OB refining furnace: ladle is transported to CAS-OB refining station, at first opens the argon gas valve and carries out the Argon stirring, then adds preliminary melting type calcium aluminate in ladle, all will carry out Argon to molten steel in the whole refining desulfuration process and stir;
(3) skim: refining desulfuration is transported to the station of skimming with ladle after finishing, and the slag that utilizes slag removal machine that rear molten steel surface is processed in desulfurization removes, and then adds ladle covering agent;
(4) refining, Alloying Treatment: at refining furnace molten steel is carried out temperature adjustment processing and stir process, liquid steel temperature should be controlled at 1570 ℃～1600 ℃ after processing finished; According to different steel grade smelting requirements, add alloy to molten steel again and carry out the alloying operation, also to carry out the argon gas stirring operation in refining and the alloying process;
(5) continuous casting: adopt the whole process protection cast.
2. application preliminary melting type calcium aluminate according to claim 1 carries out the method that the CAS-OB molten steel furnace external refining is produced low-sulfur steel, it is characterized in that: it can be silicon deoxidation, aluminium deoxidation or other conventional deoxidation modes that the deoxidation operation described in the first step requires according to steel grade.
3. application preliminary melting type calcium aluminate according to claim 1 and 2 carries out the method that the CAS-OB molten steel furnace external refining is produced low-sulfur steel, it is characterized in that: it is to adopt any one mode in floating plug, slag-blocking ball or the slag stop cone to realize that the pushing off the slag described in the first step is processed.
4. application preliminary melting type calcium aluminate according to claim 3 carries out the method that the CAS-OB molten steel furnace external refining is produced low-sulfur steel, it is characterized in that: the adding mode of the preliminary melting type calcium aluminate described in the second step can be that one or many adds molten steel, and the adding mode can be by bin blanking or artificial the input.
5. application preliminary melting type calcium aluminate according to claim 4 carries out the method that the CAS-OB molten steel furnace external refining is produced low-sulfur steel, and it is characterized in that: described preliminary melting type calcium aluminate consumption is controlled at 3～20Kg/ ton steel, and granularity is controlled at 0.1mm～100mm.
6. application preliminary melting type calcium aluminate according to claim 5 carries out the method that the CAS-OB molten steel furnace external refining is produced low-sulfur steel, and it is characterized in that: its main image of described preliminary melting type calcium aluminate consists of 12CaO7Al
2O
3, 3CaO5Al
2O
3One or more mixture, and other inevitable impurity.
7. application preliminary melting type calcium aluminate according to claim 6 carries out the method that the CAS-OB molten steel furnace external refining is produced low-sulfur steel, it is characterized in that: described Argon in the CAS-OB refining process is processed, the flow control of argon gas is at 10～500NL/min, and the treatment time is controlled at 3～20min.
8. application preliminary melting type calcium aluminate according to claim 7 carries out the method that the CAS-OB molten steel furnace external refining is produced low-sulfur steel, it is characterized in that: described skimming carried out at the station of skimming, and adopts any one equipment in vacuum dreg-sucking machine or the mechanical slag removal machine to realize.
9. application preliminary melting type calcium aluminate according to claim 8 carries out the method that the CAS-OB molten steel furnace external refining is produced low-sulfur steel, and it is characterized in that: the add-on of described ladle covering agent is controlled at 1～10Kg/ ton steel.
10. application preliminary melting type calcium aluminate according to claim 9 carries out the method that the CAS-OB molten steel furnace external refining is produced low-sulfur steel, it is characterized in that: the argon gas in described refining, the Alloying Treatment process stirs flow at 1～100NL/min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544470A (en) * | 2015-09-17 | 2017-03-29 | 鞍钢股份有限公司 | A kind of desulphurization technological process of employing CAS-OB |
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|---|---|---|---|---|
| JPS56123319A (en) * | 1980-03-04 | 1981-09-28 | Nippon Kokan Kk <Nkk> | Production of extra low sulfur steel |
| CN101168786A (en) * | 2007-11-28 | 2008-04-30 | 孙中强 | Converter steel-smelting technique |
| CN101538638A (en) * | 2009-04-15 | 2009-09-23 | 邯郸钢铁股份有限公司 | Refining method of reducing slag made by CAS refining furnace for desulfurization |
-
2012
- 2012-06-28 CN CN2012102264325A patent/CN102876848A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56123319A (en) * | 1980-03-04 | 1981-09-28 | Nippon Kokan Kk <Nkk> | Production of extra low sulfur steel |
| CN101168786A (en) * | 2007-11-28 | 2008-04-30 | 孙中强 | Converter steel-smelting technique |
| CN101538638A (en) * | 2009-04-15 | 2009-09-23 | 邯郸钢铁股份有限公司 | Refining method of reducing slag made by CAS refining furnace for desulfurization |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544470A (en) * | 2015-09-17 | 2017-03-29 | 鞍钢股份有限公司 | A kind of desulphurization technological process of employing CAS-OB |
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Application publication date: 20130116 |