CN111187901A - Method for reducing oxidation burning loss of hot-rolled steel billet in heating furnace - Google Patents
Method for reducing oxidation burning loss of hot-rolled steel billet in heating furnace Download PDFInfo
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- CN111187901A CN111187901A CN201911322310.4A CN201911322310A CN111187901A CN 111187901 A CN111187901 A CN 111187901A CN 201911322310 A CN201911322310 A CN 201911322310A CN 111187901 A CN111187901 A CN 111187901A
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D11/00—Process control or regulation for heat treatments
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/70—Furnaces for ingots, i.e. soaking pits
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
- C23C8/16—Oxidising using oxygen-containing compounds, e.g. water, carbon dioxide
- C23C8/18—Oxidising of ferrous surfaces
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- Mechanical Engineering (AREA)
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- Metallurgy (AREA)
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Abstract
The invention belongs to the field of billet heating, and provides a method for reducing oxidation burning loss of hot-rolled billets in a heating furnace. The method comprises the steps of heating a steel billet in a low-temperature furnace at 500-560 ℃ before the steel billet enters a high-temperature furnace, introducing oxygen-enriched air into the low-temperature furnace, wherein the oxygen concentration in the oxygen-enriched air is 50-70%, the heating time is 10-50 min, and rapidly forming a layer of compact Fe on the surface of the steel billet by oxygen enrichment, low-temperature and short-time heating3O4Scale protective film, the dense Fe after entering the high temperature furnace3O4The oxide film blocks the contact of air and the internal structure of the billet, thereby inhibiting the further oxidation of the billet, and compared with the traditional heating method, the method reduces the thickness of the oxide scale by more than 50 percent.
Description
Technical Field
The invention relates to the technical field of steelmaking energy conservation, in particular to a method for reducing oxidation burning loss of hot-rolled steel billets in a heating furnace.
Background
By 2018, the steel yield in China reaches 8 hundred million tons, wherein the hot rolled steel capacity exceeds 5 hundred million tons/year, and the hot rolled steel has various types, such as plate strips, construction steel bars, seamless steel pipes, various profiles and the like. The production process of hot rolled steel needs heating many times, after the continuous casting billet is produced, heating is needed when rough rolling is cogging, and the middle rolling process also needs heating for many times, in order to reduce rolling force, heating is generally needed to be carried out to 1100-1250 ℃, the heating time is 0.5-3 h, and oxide skin is formed on the surface of the steel billet during each heating, so that oxidation burning loss is generated, and the oxidation burning loss is 1-2.5%. Calculated according to the average burning loss of 1.5 percent, if the oxidation burning loss can be reduced by 50 percent, 750 million tons of hot rolled steel can be saved every year, and calculated according to the average 4000 yuan/ton of the hot rolled steel, 300 million yuan can be saved, thereby having great economic benefit and social benefit.
Because a steel mill can generate a byproduct of coal gas in the processes of coking, ironmaking and steelmaking, hot rolled steel is generally heated by coal gas, steel billets are generally directly fed into a high-temperature coal gas heating furnace for heating, and the heating temperature is generally in the range of 1100-1250 ℃ according to different steel types. According to the difference of the thickness and the steel type of the steel billet, the heating time is different from 0.5 to 3 hours each time, long-time heating is carried out at high temperature, the oxidation burning loss is very serious, the general burning loss can reach 1 to 2.5 percent, and the loss of a steel mill is huge, so that a steel billet heating process capable of reducing the oxidation burning loss is urgently needed by a hot rolling steel mill.
Therefore, the invention provides a process method for reducing the oxidation burning loss of hot-rolled steel billets.
Disclosure of Invention
The invention aims to solve the problems of large oxidation burning loss of the heating surface of a steel billet, large energy consumption and the like in the prior art, and provides a method for reducing the oxidation burning loss of a hot-rolled steel billet in a heating furnace.
Iron and oxygen react at a certain temperature, possibly generating Fe2O3FeO and Fe3O4Three oxide products, which differ greatly in their properties, wherein:
FeO is a p-type oxide semiconductor, and the layer has higher cation vacancy concentration, so that the mobility of cations and electrons in the FeO layer is very high, and the FeO layer has fast growth rate, is black, has a loose structure and is easy to fall off.
Fe3O4Is also a p-type oxide semiconductor, which is more stoichiometric than FeO and thus unfavorable for Fe2+And (4) diffusion. Fe3O4From one Fe2+And two Fe3+Composition of spinel structure, Fe2+And Fe3+In tetrahedral and octahedral interstitial positions, respectively, Fe3O4Is black and gray, has compact texture and tight combination, and can play a role in protection.
Fe2O3The n-type oxide semiconductor has high oxygen content, has a plurality of oxygen ion defects inside, forms anion vacancies and is beneficial to the diffusion of oxygen inside the outside. Fe2O3gamma-Fe having two crystal structures, metastable at low temperature2O3Cubic crystal α -Fe with rhombohedral structure above 400 deg.C2O3，Fe2O3Commonly known as hematite, is reddish brown.
From this, we know that Fe3O4Compact texture and tight combination, while FeO has a loose structure and Fe2O3The density is between Fe3O4And FeO. In the initial stage of heating billet, if a compact Fe layer can be rapidly generated3O4The layer can protect the steel billet and prevent oxygen from contacting the internal structure of the steel billet, thereby preventing further oxidation.
According to the equilibrium diagram of the iron-oxygen reaction, when pure iron is below 567 ℃, Fe in the generated oxidation product3O4With the lowest Gibbs free energy, i.e. Fe in the oxidation product3O4Most stable and the thermodynamic tendency of the formation is greatest, i.e. below 567 ℃, Fe is formed3O4Is the most likely; at temperatures above 567 deg.C, the Gibbs free energy for FeO formation is lowest, and at this time FeO in the oxidation product is most stable and the thermodynamic tendency for formation is greatest.
The heating temperature of the general steel billet is 1100-1250 ℃, and at the moment, the formed oxide layer has a three-layer structure which is specially characterized in thatThin Fe2O3Outer layer of slightly thicker Fe3O4The thickness ratio of the three oxides is approximately 1:4:9, the inner layer is loose FeO, the bonding force with a steel matrix is weak, the FeO is easy to peel off, the protection effect cannot be formed, and the oxidation is easy to advance to the interior of the steel billet.
Therefore, if a dense Fe layer can be formed on the surface of the billet in a short time3O4The oxide film, when forming a protective layer, can block the progress of oxidation to the inside of the billet, and Fe is generated at 567 ℃ or lower according to the equilibrium diagram of iron-oxygen reaction3O4Has the lowest Gibbs free energy, Fe3O4Is a stable phase. The traditional hot rolling billet heating directly sends the billet into a high-temperature furnace for heating, so the low-temperature heating prefabricated Fe is added between the billet entering the high-temperature furnace3O4The procedure of oxide skin, according to the iron-oxygen equilibrium diagram, the heating temperature needs to be lower than 567 ℃ to generate Fe stably3O4On the other hand, if the heating temperature is too low, the oxidation reaction time is too long, so the heating temperature is not lower than 500 ℃.
Therefore, the invention discloses a method for reducing the oxidation burning loss of a hot-rolled steel billet in a heating furnace, wherein the steel billet is preheated in a low-temperature furnace before being heated in a high-temperature furnace, so that a layer of compact Fe is quickly formed on the surface of the steel billet3O4The oxide film is used for preventing air from permeating into the steel billet, so that the oxidation burning loss is reduced; wherein the content of the first and second substances,
the billet steel is heated in a low-temperature furnace by adopting coal gas, the preheating temperature is 500-560 ℃, oxygen-enriched air is introduced into the low-temperature furnace in the heating process, and the oxygen volume concentration in the oxygen-enriched air is 50-70% of the oxygen-enriched air.
Further, the heating time of the steel billet in the low-temperature furnace is 10-50 min.
Further, the billet is preheated in a low-temperature furnace firstly, and Fe is prefabricated3O4Film-oxidizing and thenSending the mixture into a high-temperature furnace to be heated to the rolling temperature.
Further, the billet is prefabricated into Fe in a low-temperature heating furnace at 500-560 DEG C3O4After the film is oxidized, the Fe of the billet is burnt in a high-temperature furnace at 1100-1250 ℃ to ensure that the Fe of the billet is removed3O4The oxide film thickness is reduced by at least 50%.
To generate Fe in a short time3O4The oxide film layer is characterized in that Fe is completely generated at a ferrite atomic ratio of Fe to O of 42.66 to 57.34 at a temperature of 567 ℃ or lower according to an iron-oxygen reaction equilibrium diagram3O4If the atomic ratio is less than this, Fe atoms are excessive, so that Fe can be rapidly produced3O4The oxide film layer needs higher oxygen concentration, the oxygen concentration in the air is only 21 percent, oxygen or oxygen-enriched air needs to be blown manually, the oxygen concentration in the oxygen-enriched air is not lower than 50 percent, the oxygen concentration is not too high, the oxygen concentration is more than 70 percent, the oxygen is excessive, and the excessive oxygen can lead Fe3O4Is oxidized into Fe2O3The density is lower than that of Fe3O4Therefore, the oxygen concentration is not higher than 70%. Therefore, the volume concentration of the oxygen is 50-70% of the oxygen-enriched air.
To generate Fe on the surface of the billet3O4The oxide film layer needs a certain reaction time, under the action of high-concentration oxygen, the reaction time is generally between 10 and 50min and less than 10 min, and Fe3O4The thickness of the oxide film is thin, and is higher than 50min, then Fe3O4The oxide film is too thick.
If the steel billet has the oxide skin formed at high temperature before entering the low-temperature furnace, the steel billet needs to be descaled by a high-pressure water gun firstly to remove loose oxide skin mainly containing FeO, and then the steel billet is sent into the low-temperature furnace to perform scale pre-treatment. The hot rolling steel billet is generally cast by a continuous casting method, a layer of scale mainly comprising FeO is generated in the continuous casting process, after descaling by a high-pressure water gun, an FeO oxide film remained on the surface of the steel billet is kept at 500-567 ℃ according to a Fe-O reaction constant-temperature transformation phase diagram, and because the FeO phase is an unstable phase in the temperature range, Fe3O4Is a stable phase, so after a certain time of heat preservation, the FeO oxide film can be oxidized into Fe3O4According to the test results, Fe can be generated under the condition of oxygen-enriched air (the oxygen content is more than 50 percent and less than 70 percent) and the heat preservation time is more than 20min3O4And (3) a layer.
The low-temperature oxygen-enriched prefabricated Fe prepared by the method3O4The oxide skin method can form a compact protective layer with the thickness of 0.05-0.2 mm on the surface of the steel blank after 10-50 min of treatment, so that the contact between oxygen and a steel matrix is blocked, further oxidation is inhibited, and the oxidation burning loss is reduced.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the traditional anti-oxidation technology, the traditional anti-oxidation method avoids oxide skin formation as much as possible, so that inert gases such as nitrogen, argon and the like are adopted for protection, a furnace body is required to be sealed, the structure is complex, and continuous production is difficult to realize;
2. compared with the traditional heating aspect that the hot rolled steel billet is directly placed into a high-temperature furnace to be heated to 1100-1250 ℃, the low-temperature oxygen-enriched prefabricated oxide skin heating technology can form a layer of compact oxide skin on the surface of the steel billet and inhibit further oxidation burning loss in the high-temperature heating stage, thereby greatly reducing the oxidation burning loss in the steel billet heating process of a steel rolling mill, saving steel, reducing cost and improving benefit;
3. prefabricated compacted Fe according to the invention3O4The oxide layer method is simple and easy to implement, the oxide layer prefabricating process is also a billet preheating process, and energy is not lost;
4. the heating method is simple and easy to implement, does not need to make great modification on the existing heating equipment of a steel mill, and only needs to add a low-temperature heating furnace.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments for implementing technical means and features of the present invention, however, the present invention is not limited to these embodiments.
The invention performs the prefabrication of compact Fe by low-temperature and oxygen-enriched heating3O4The oxidation layer forming process includes preheating the steel billet in a low temperature furnace before heating in a high temperature furnace to form one compact Fe layer on the surface3O4The oxide film is used for preventing air from permeating into the steel billet, so that the oxidation burning loss is reduced; the billet steel is heated in a low-temperature furnace by adopting coal gas, the preheating temperature is 500-560 ℃, oxygen-enriched air is introduced into the low-temperature furnace in the heating process, the oxygen volume concentration of the oxygen-enriched air is 50-70% of the oxygen-enriched air, and the heating time is 10-50 min. The heating time is short for ordinary carbon steel, and is properly prolonged for high-alloy steel such as stainless steel, and oxygen-enriched air is introduced during heating, wherein the oxygen concentration is 50-70%. Before the billet is sent into the low-temperature heating furnace, if the surface of the billet has an oxide scale layer, firstly a high-pressure water gun is used for descaling, the oxide scale on the surface is cleaned, then the billet is sent into the low-temperature prefabricated oxide scale heating furnace, and for the residual FeO on the surface, in the low-temperature oxygen-enriched heat preservation process, the residual FeO layer can be converted into Fe3O4. After the heating of the billet steel in the low-temperature furnace is finished, the billet steel is quickly transferred to the high-temperature furnace for heating, and the billet steel is heated according to a common heating schedule.
Prefabricated Fe3O4The layer can prevent oxidation from advancing to the inside of the steel billet to a great extent, but can not completely stop the oxidation activity of the steel billet, and the Fe is prefabricated3O4When the steel billet of the protective layer is transferred into a high-temperature gas heating furnace with the heating temperature of 1100-1250 ℃ for heating, FeO and Fe with certain thickness can be generated2O3And Fe3O4Oxide scale of the composition.
The concrete application is shown in the following examples, in the following application examples, FeO and Fe2O3、Fe3O4The phase analysis of (2) was measured by an X-ray diffractometer (XRD) and an Electron Back Scattering Diffraction (EBSD) method. The thickness of the oxide skin is measured by adopting a scanning electron microscope and is along the longitudinal direction of the oxidized billetAnd (4) after the saw cutting sample is subjected to grinding and polishing, the thickness of the surface oxide scale is measured by adopting a scanning electron microscope.
Example 1
A stainless steel 0Cr19Ni9 billet having a thickness of 100mm and a width of 150mm was heated for the purpose of separately measuring the amount of prefabricated Fe3O4Protecting layer and final oxide skin thickness, simultaneously heating two steel billets in a low-temperature furnace, immediately cooling one steel billet after heating, sampling and measuring prefabricated Fe3O4And (5) the thickness of the protective layer is changed into a high-temperature furnace for heating immediately after the other protective layer is heated. The heating temperature of coal gas in the low-temperature furnace is 560 ℃, the heating time is 20min, and oxygen-enriched air is introduced during heating, wherein the oxygen concentration in the oxygen-enriched air is 50%. Heating in a low temperature furnace for 20min, taking out one of the billets immediately, cooling to room temperature by water spraying, sampling, measuring the prefabricated Fe3O4Thickness of layer, measured as Fe3O4The thickness of the protective layer is 0.05 mm; and another one is immediately transferred into a high-temperature heating furnace for heating at 1200 ℃ for 1h, after heating is finished, the temperature of the steel billet is cooled to room temperature by adopting water spraying, and the thickness of the oxide scale is measured to be 0.15 mm.
Comparative example 1
Heating stainless steel 0Cr19Ni9 steel billet with thickness of 100mm and width of 150mm, directly feeding the steel billet into a high-temperature furnace for heating at 1200 ℃, heating for 1h, cooling the steel billet to room temperature by water spray after heating, and measuring the thickness of the oxide scale to be 0.50 mm.
Example 2
Heating a round bar of GCr15 steel with a billet diameter of 150mm for the respective measurement of the prefabricated Fe3O4Simultaneously heating two bar blanks in a low-temperature furnace to obtain a protective layer and final oxide skin thickness, immediately cooling one bar blank after heating, sampling and measuring prefabricated Fe3O4And (4) immediately turning to a high-temperature furnace for heating after the other heating layer is heated. The heating temperature of the coal gas in the low-temperature furnace is 530 ℃, the heating time is 35min, and oxygen-enriched air is introduced during heating, wherein the oxygen concentration in the oxygen-enriched air is 60%. Heating in a low temperature furnace for 35min, and taking one steel bar immediatelyTaking out, cooling to room temperature by adopting water spraying, and measuring the prefabricated Fe after sampling3O4Thickness of layer, measured as Fe3O4The thickness of the protective layer is 0.1 mm; and another steel bar is immediately transferred into a high-temperature heating furnace to be heated at 1200 ℃, the heating time is 1.2h, after the heating is finished, the temperature of the steel billet is cooled to room temperature by adopting water spraying, and the thickness of the oxide scale is measured to be 0.23 mm.
Comparative example 2
Heating bearing steel GCr15 round bar billet with billet diameter of 150mm, directly feeding into a high temperature furnace for heating at 1200 deg.C for 1.2h, cooling the billet to room temperature by water spray after heating, and measuring oxide scale thickness of 0.62 mm.
Example 3
Heating a common carbon steel Q235 billet with a thickness of 250mm and a width of 300mm for respectively measuring the prefabricated Fe3O4Protecting layer and final oxide skin thickness, simultaneously heating two steel billets in a low-temperature furnace, immediately cooling one steel billet after heating, sampling and measuring prefabricated Fe3O4And (5) the thickness of the protective layer is changed into a high-temperature furnace for heating immediately after the other protective layer is heated. Firstly, heating by using coal gas in a low-temperature furnace at 500 ℃ for 50min, and introducing oxygen-enriched air during heating, wherein the oxygen concentration in the oxygen-enriched air is 70%. Heating in a low temperature furnace for 50min, taking out one of the billets immediately, cooling to room temperature by water spraying, sampling, measuring the prefabricated Fe3O4Thickness of layer, measured as Fe3O4The thickness of the protective layer is 0.2 mm; and the other block is immediately transferred into a high-temperature furnace for heating, the heating temperature is 1250 ℃, the heating time is 1.5h, after the heating is finished, the temperature of the billet is cooled to room temperature by adopting water spraying, and the thickness of the oxide scale is measured to be 0.3 mm.
Comparative example 3
Heating a common carbon steel Q235 billet with the thickness of 250mm and the width of 300mm, directly feeding the billet into a high-temperature furnace for heating at the temperature of 1250 ℃ for 50min, cooling the billet to room temperature by adopting water spraying after heating is finished, and measuring the thickness of an oxide scale to be 0.83 mm.
And (3) analyzing an experimental result:
comparing example 1 with comparative example 1, for stainless steel 0Cr19Ni9, compared with the traditional direct high temperature heating process, the low temperature, oxygen-enriched preheating process of the invention can reduce the oxide scale thickness from 0.5mm to 0.15mm, and the reduction of oxidation burning loss reaches 70%.
Comparing example 2 with comparative example 2, for GCr15 steel billet, compared with the traditional direct high temperature heating process, the low temperature, oxygen-enriched preheating process of the invention can reduce the oxide scale thickness from 0.62mm to 0.23mm, and the reduction of oxidation burning loss reaches 62.9%.
Comparing example 3 with comparative example 3, for the common carbon steel Q235 billet, compared with the traditional direct high-temperature heating process, the low-temperature oxygen-enriched preheating process can reduce the thickness of the oxide skin from 0.83mm to 0.3mm, and the reduction range of the oxidation burning loss reaches 63.8 percent.
Therefore, the method has very obvious effect on reducing the oxidation burning loss.
The above embodiments are merely preferred examples of the present invention, and not intended to limit the scope of the invention, so that equivalent changes or modifications in the structure, features and principles described in the claims of the present invention should be included in the claims of the present invention.
Claims (5)
1. A method for reducing the oxidation burning loss of hot-rolled steel billet in heating furnace features that before the steel billet is heated in high-temp furnace, the steel billet is preheated in low-temp furnace to quickly form a compact Fe layer on its surface3O4The oxide film is used for preventing air from permeating into the steel billet, so that the oxidation burning loss is reduced; wherein the content of the first and second substances,
the billet steel is heated in a low-temperature furnace by adopting coal gas, the preheating temperature is 500-560 ℃, oxygen-enriched air is introduced into the low-temperature furnace in the heating process, and the oxygen volume concentration in the oxygen-enriched air is 50-70% of the oxygen-enriched air.
2. The method for reducing oxidation burn-out of a hot rolled steel slab in a furnace of claim 1 wherein said slab is heated in a cryogenic furnace for a time period of 10 to 50 minutes.
3. The method of reducing oxidation burn-out in a hot rolled steel slab in a furnace of claim 1 wherein said slab is first preheated in a cryogenic furnace, with Fe pre-cast3O4Oxidizing the film, and then feeding the film into a high-temperature furnace to be heated to a rolling temperature.
4. The method for reducing oxidation burning loss of a hot rolled steel slab in a heating furnace according to claim 1, wherein dense Fe with a thickness of 0.05 to 0.2mm is formed on the surface of the steel slab after preheating in a low temperature furnace3O4And (5) oxidizing the film.
5. A method for reducing oxidation burn-out in a hot rolled steel slab as claimed in any one of claims 1 to 3 wherein said slab is first preformed to Fe in a low temperature furnace at a temperature of 500 ℃ to 560 ℃3O4After the film is oxidized, the film is heated in a high-temperature coal gas heating furnace at 1100-1250 ℃, and Fe is compacted with the traditional non-prefabricated Fe3O4Compared with the heating method of the oxide film, the thickness of the oxide layer of the billet heated by the method is reduced by at least 50 percent.
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| CN113106225A (en) * | 2021-03-31 | 2021-07-13 | 北京首钢股份有限公司 | Method for reducing intercrystalline oxidation depth of high-carbon tool steel |
| CN115612973A (en) * | 2022-11-02 | 2023-01-17 | 上海大陆天瑞激光表面工程有限公司 | Laser high-temperature flash forming method for surface oxide film of steel material |
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