Manufacturing process for raw material steel and assembly for its manufacture
The described process addresses the challenges of high CO2 emissions and nitrogen content in steel production by using a melting furnace with arc resistance and a converter, achieving low-nitrogen crude steel production efficiently and cost-effectively, suitable for ULC and IF steel grades.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2021-08-03
- Publication Date
- 2026-04-02
AI Technical Summary
The existing steelmaking processes, namely the blast furnace - converter route and electric steel route, face challenges in reducing CO2 emissions and nitrogen content in crude steel, which affects the production of ultra-low carbon (ULC) and interstitial-free (IF) steel grades, requiring complex and costly secondary metallurgical processes.
A process involving a melting furnace with arc resistance followed by a converter, where reduced iron and scrap are melted in a reducing atmosphere, and the molten metal is refined with oxygen to produce low-nitrogen crude steel, utilizing a submerged probe and inert gas to enhance denitrification, while maintaining a reducing atmosphere to form CO bubbles for nitrogen removal.
This process effectively reduces nitrogen content to 50 ppm or less, minimizing CO2 emissions and capital costs, enabling the production of ULC and IF steel grades without the need for additional investments in secondary metallurgical equipment.
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Abstract
Description
Technical Field
[0001] In modern steelmaking, essentially two different routes are used, namely, first, the blast furnace - converter route, and second, the electric steel route. In the blast furnace - converter route, iron ore is reduced and melted in a blast furnace by adding coke. Subsequently, the obtained molten metal is oxidized ("refined") by oxygen in an oxygen converter. Thereby, trace elements having an oxygen affinity in the molten metal (e.g., carbon, silicon, manganese, phosphorus), which are discharged in the form of gas or slag, are oxidized. In the electric steel route, the starting materials used are, in some cases, direct reduced iron in briquette form ("iron sponge"), and / or scrap. This starting material is melted in an electric arc furnace, and similarly, components having an oxygen affinity can be removed by blowing oxygen. See, for example, WO 2004 / 108971.
[0002] The blast furnace - converter route has the drawback that the reduction by coke in the blast furnace releases a very large amount of CO2. In contrast, the electric steel route generally has the drawback that the removal efficiency of elements having an oxygen affinity and impurities introduced by scrap is low. In the electric steel route, the levels of trace elements and impurities have to be further reduced by complex downstream secondary metallurgical processes. Therefore, the electric steel route is essentially used for construction steels and long products where a relatively high content of trace elements is tolerated.
[0003] For example, crude steel having a low content of trace elements, which functions as a starting material for ULC steel grades such as IF steel and non - oriented electromagnetic strip, is produced almost exclusively via the blast furnace - converter route. Therefore, steelworks have appropriate assemblies in place in general to produce suitable crude steel in the required volumes and further process it.
[0004] The ULC (ultra - low carbon) steel grade is understood to mean a steel grade having a carbon content C of 150 ppm or less (0.015 wt%), particularly 100 ppm or less, preferably 50 ppm or less, particularly 30 ppm or less.
[0005] IF steel is understood to mean a ULC steel grade that further has a nitrogen content of 50 ppm or less (0.005 wt%), preferably 30 ppm or less.
[0006] The term "non-oriented electromagnetic strip grade" is understood to mean IF steel further containing 1.0 to 5.0%, preferably 2.0 to 4.0%, of silicon (Si).
[0007] The elemental content mentioned for steel grades is based, for example, on solidified steel after casting in a continuous casting plant.
[0008] This specification places particular emphasis on the nitrogen content of the manufactured crude steel, because, as will be explained in detail later, the nitrogen content can only be reduced with difficulty by secondary metallurgy, especially when the oxygen content exceeds a certain level at the same time. [Prior art documents] [Patent Documents]
[0009] [Patent Document 1] International Publication No. 2004 / 108971 [Overview of the Initiative] [Problems that the invention aims to solve]
[0010] Therefore, an object of the present invention is to provide a process for producing low-nitrogen crude steel that reduces CO2 emissions and allows the maximum number of existing assemblies to be used to minimize capital costs in the technological transition. [Means for solving the problem]
[0011] This process for producing low-nitrogen crude steel includes at least the following process steps: A process of directly melting reduced iron and / or scrap in a melting furnace that has arc resistance, particularly one with a reducing atmosphere, to obtain a molten metal and slag. • The process of removing the molten metal from the melting furnace and using it to fill the converter. - A process of refining a molten metal in a converter to obtain liquid crude steel, and then tapping out liquid crude steel having a nitrogen content of 70 ppm or less, and especially 50 ppm or less.
[0012] Intermediate treatment, particularly desulfurization of the molten metal, may be performed after the molten metal has been removed from the melting furnace and before the converter is filled.
[0013] Alternatively or additionally, the intermediate treatment may include slag removal and / or desilicate.
[0014] This method offers numerous technical and economic benefits, which will be explained in detail below.
[0015] The present invention further relates to an assembly for carrying out such a process. The assembly comprises a melting furnace having arc resistance for producing a metal molten body, and a converter located downstream of the melting furnace for refining the metal molten body to obtain liquid crude steel. In certain embodiments, a desulfurization plant is located immediately downstream of the melting furnace, and the converter is located immediately downstream of the desulfurization plant.
[0016] In the context of this application, “immediately downstream” and “immediately upstream” mean that the respective plants are directly adjacent to each other. What takes place between such directly adjacent plants is the transport of materials and / or intermediate storage of materials. More specifically, between two such plants, the materials are not refined, mixed with other substances, or otherwise improved.
[0017] The following rules are used when describing elemental content: An element symbol in square brackets (e.g., "[N]") indicates the weight percentage content of that element (in this case, nitrogen) in the molten metal. An element symbol in parentheses (e.g., "(P)") indicates the weight percentage content of that element (in this case, phosphorus) in the slag. An element symbol without parentheses (e.g., "C") means the weight percentage content of that element (in this case, carbon) in the cast steel.
[0018] In this application, unless otherwise specified, percentages (or ppm values) should be considered as percentages by weight.
[0019] Different types of electric heating plants for melting metals or heating liquid metals are distinguished as follows: 1. An electric arc furnace (EAF) that forms an arc between an electrode and a metal. This includes AC electric arc furnaces (EAFac), DC electric arc furnaces (EAFdc), and ribe furnaces (LF).
[0020] 2. A melting furnace with arc resistance that forms an arc between an electrode and a charge or slag, or heats the charge or slag by the Joule effect. This includes, firstly, buried electric arc furnaces (SAFs) in which the electrode is embedded in the charge or slag, such as AC buried arc furnaces (SAFac) and DC buried arc furnaces (SAFdc). Secondly, this also includes furnaces in which the electrode can be terminated directly above the slag. In this type of furnace, the slag is not shielded by the charge, at least within the area of the electrode. Thus, the slag is open at the top, and the brush arc formed in the slag can be seen from above. This type of furnace is also called an open slag bath furnace (OBSF).
[0021] An electric arc furnace is operated in an oxidizing atmosphere to burn undesirable trace elements. In contrast, a melting furnace with arc-resistant heating is operated in a reducing atmosphere.
[0022] In the first step of the process, direct reduced iron and / or scrap is melted in a melting furnace with arc-resistant heating to obtain a metal melt, and at the same time slag is formed.
[0023] According to the present invention, following the treatment in a melting furnace with arc-resistant heating, a metal melt for charging into a converter is used, and the metal melt is refined in the converter to obtain liquid crude steel. In particular, the refining involves spraying oxygen of industrial grade purity onto the metal melt from above the metal melt using a submerged probe, particularly 30 - 80 m 3 (STP) (standard cubic meter) of oxygen of industrial grade purity, preferably 40 - 60 m per ton of the metal melt 3 (STP) of oxygen of industrial grade purity. The oxygen is sprayed onto the metal melt over a period of 10 - 40 minutes. The period is preferably at least 12 minutes, more preferably at least 15 minutes. Separately from this, the period is preferably 35 minutes or less, more preferably 30 minutes or less.
[0024] As is well known, a converter is used for the oxidative removal of trace elements. This is particularly true for carbon, in the converter, the metal melt is converted to crude steel having a carbon content [C] of 600 ppm or less, preferably 500 ppm or less. In particular, the carbon content [C] of the starting steel is at least 200 ppm, preferably at least 300 ppm. In this specification, the converter particularly takes the form of an oxygen converter.
[0025] In the subsequent secondary metallurgical treatment of the produced crude steel, which will be described in more detail later, the carbon content [C] of the crude steel is further reduced to a carbon content C of the ULC steel grade of 150 ppm or less, particularly 100 ppm or less, preferably 50 ppm or less, particularly 30 ppm or less.
[0026] The oxygen converter, also known in technical terms as the Linz-Donauwitz converter (LD converter), includes a tiltable converter vessel lined with refractory lining.
[0027] The molten metal drawn from the melting furnace is used to fill the converter. The converter may be further filled with scrap metal that acts as a coolant. It may also be possible to add pig iron from the blast furnace process. This is the case, for example, during the modification of an existing assembly.
[0028] The molten metal is refined within the converter. This involves blowing oxygen onto the molten metal using a retractable water-cooled probe. The subsequent vigorous initiation of oxidation of iron and trace elements, after a blowing time of 10-40 minutes, has the effect of reducing the trace elements to the desired level and melting the scrap used. The burnt iron by-products either escape as gas or bind in the liquid slag with the lime added at this stage.
[0029] As with the reduction of undesirable trace elements, the exothermic reaction with the blown-in oxygen ensures the swirling of the molten material, thereby improving the outcome of the purification process and shortening the processing time. To further enhance this mixing, it is possible to blow in an inert gas, typically argon and nitrogen, through a nozzle inserted into the base of the converter. According to the present invention, purification also reduces the nitrogen content, as described below. For this reason, argon is preferred as the inert gas used in the mixing. Alternatively, the nitrogen content is reduced during purification with the inert gas, resulting in only a small amount of nitrogen present, if any, in the inert gas towards the end of the purification process.
[0030] Similar to other processes described later, CO bubbles are formed in the metal molten material by the oxidation of carbon as a trace element. Due to the low partial pressure of nitrogen within the CO bubbles, the nitrogen [N] dissolved in the metal molten material diffuses into the CO bubbles, leaving the molten material with the CO. This denitrification process proceeds as long as CO bubbles are formed, i.e., as long as there is enough carbon in the metal molten material to be oxidized to CO. Therefore, the denitrification process is favorable when the metal molten material has a carbon-to-nitrogen content ratio [C] / [N] of at least 20, preferably at least 100, particularly at least 200, even more preferably at least 500, and particularly at least 1000 immediately before purification.
[0031] In a preferred embodiment, the carbon content [C] of the metal molten material immediately before purification is at least 1.0%, preferably at least 1.5%, and more preferably at least 2.0%. In a further preferred embodiment, the carbon content [C] of the metal molten material immediately before purification is 5.0% or less, preferably 4.5% or less, and more preferably 4.0% or less.
[0032] These described carbon content [C] and high carbon-to-nitrogen content ratio [C] / [N] make it possible to achieve effective denitrification, such that even if the nitrogen content [N] of the metal molten material immediately before refining is up to 450 ppm, the liquid crude steel dispensed after refining has a nitrogen content [N] of 50 ppm or less, preferably 40 ppm or less, particularly 30 ppm or less, even more preferably 25 ppm or less, and particularly 20 ppm or less.
[0033] Converters are often in a largely closed configuration to reduce, and especially to completely prevent, the reintroduction of nitrogen from the ambient atmosphere. This is further aided by the formation of CO. The amount of CO is so large that the ambient air is displaced at the surface of the molten material, suppressing the uptake of nitrogen from the ambient air.
[0034] In secondary metallurgical processes and / or casting of crude steel, some nitrogen may be incorporated, so in the refining operation of the converter, it is advantageous to reduce the nitrogen content significantly more than is actually required for the steel grade to be achieved. For example, in the production of IF steel grades having a nitrogen content of 30 ppm or less N, the nitrogen content [N] of the liquid crude steel after refining is reduced to a maximum of 25 ppm, preferably a maximum of 20 ppm.
[0035] The process of the present invention described herein, firstly, enables the successful reduction of the nitrogen content of the molten metal when the nitrogen content exceeds 50 ppm, and secondly, enables the low or further reduction of the nitrogen content when the nitrogen content is less than 50 ppm. As a result, the nitrogen content [N] of the refined liquid crude steel is 50 ppm or less in both cases.
[0036] In preferred embodiments, the carbon content [C] of the molten metal increases in the melting furnace and / or converter. Thus, the carbon content increases before purification in the converter. This helps ensure that sufficient CO bubbles are formed during purification to enable an efficient denitrification process. In particular, the carbon content [C] of the molten metal increases immediately before purification to such an extent that there exists a carbon-to-nitrogen content ratio [C] / [N] of at least 20, preferably at least 100, especially at least 200, even more preferably at least 500, especially at least 1000.
[0037] The carbon content [C] of a molten metal is achieved, in particular, by blowing coke or process gas / dust into the melting furnace or converter.
[0038] In preferred embodiments, the iron content (Fe) of the slag in the melting furnace is less than 30% by weight, preferably less than 20% by weight. This results in particularly low iron loss through the slag, making the process particularly efficient. Such low iron content can be achieved, in particular, by using a melting furnace with arc protection. In electric arc furnaces operated under oxidizing conditions, the oxidizing atmosphere further increases yield loss in the form of FeO in the slag, meaning that the use of this type of melting furnace is not very efficient. Therefore, combining a melting furnace with arc protection with a downstream converter is more efficient for physical purposes than an electric arc furnace that combines melting and oxidation in a single step. Furthermore, if the arc is not sufficiently shielded by the foamed slag, energy loss is high in an electric arc furnace, so a melting furnace with arc protection is more energy efficient.
[0039] In a more preferred embodiment, the melting furnace with arc resistance is in a closed configuration. This firstly prevents heat loss and further reduces the introduction of oxygen, resulting in a reduced furnace atmosphere being maintained and thus low oxidation loss.
[0040] In secondary metallurgy, another means of reducing nitrogen content is vacuum treatment (e.g., Ruhrstahl-Heraeus process, RH process). However, this is only possible to a limited extent in the production of ULC steel grades. For ULC steel grades, extremely low carbon content of 150 ppm, particularly 50 ppm, preferably 30 ppm, is achieved by refining in the converter and downstream secondary metallurgical treatment (vacuum treatment in this case). However, this refining operation simultaneously enriches the dissolved oxygen in the crude steel. The oxygen content [O] in the crude steel downstream of the converter is 300-2300 ppm. In particular, the oxygen content is at least 400 ppm, preferably at least 600 ppm, and more preferably at least 800 ppm. In particular, the oxygen content is 2100 ppm or less, preferably 2000 ppm or less, and more preferably 1800 ppm or less. However, the effect of this oxygen content is that denitrification to a specified nitrogen content [N] of 50 ppm or less by vacuum treatment does not proceed efficiently. Studies have shown that such vacuum denitrification is only economically feasible within a reasonable timeframe when the minimum oxygen content [O] is 100 ppm or less.
[0041] In secondary metallurgy, vacuum denitrification would introduce further problems. Firstly, it would require additional investment for the corresponding assembly. Secondly, in the manufacture of steel grades, modifying the secondary metallurgical method would necessitate redefining the manufacturing process for the end customer. The process of the present invention for the manufacture of crude steel has the added advantage of not requiring recertification, as further improvements in secondary metallurgy remain unchanged.
[0042] Therefore, the process of the present invention can simultaneously produce low-nitrogen crude steel, which is particularly low in carbon and thus can be used as a starting product for the production of ULC steel grades. In particular, the carbon content of the crude steel is less than 600 ppm, preferably less than 500 ppm, and the nitrogen content is less than 50 ppm, preferably less than 30 ppm.
[0043] In conventional electrical steel processes using electric arc furnaces, oxygen is also blown in, particularly to remove carbon, but due to the furnace design, the amount of oxygen that can be introduced is limited, so the carbon content cannot be reduced to a significant degree. The relatively small amount of oxygen introduced during refining also means that conventional electrical steel processes do not have the efficient denitrification via CO bubbles described. Secondly, since this type of melting furnace operates using an oxidizing atmosphere (i.e., under ambient air), nitrogen is introduced from the ambient atmosphere. Furthermore, such furnaces have a flat design that further facilitates nitrogen introduction, in contrast to converters.
[0044] A further advantage of the process of the present invention is the low silicon content of the liquid crude steel after tapping in the converter. During refining in the converter, silicon is oxidized very effectively and subsequently removed by the slag, so the Si content upstream of the converter is irrelevant. The Si content of the tapped liquid crude steel is 300 ppm or less, preferably 200 ppm or less.
[0045] For typical starting materials, the Si content [Si] of the molten metal at the time of filling the converter can be up to 1.5%.
[0046] A further advantage of the process of the present invention, which uses a converter, over conventional electrical steel processes using electric arc furnaces, lies in the slag content. While a converter can achieve a slag content of 100-120 kg / t, an electric arc furnace achieves only about 50 kg / t. Furthermore, the increased standard volumetric flow rate during refining in the converter results in significant mixing of the slag and molten material. As a result, an emulsion of molten droplets in the slag is obtained. This increases the reactive surface area between the molten material and the slag, which has a positive effect on dephosphorization. Moreover, the deposition of phosphorus as P2O5 in the slag is an equilibrium reaction. Therefore, achieving the maximum slag content is advantageous when the maximum amount of phosphorus from the molten material is deposited in the slag. Using a converter, a phosphorus distribution (P) / [P] = 60-80 wt% / wt% can be obtained, while in an electric arc furnace, the same ratio is only 30-40 wt% / wt%. Furthermore, in the case of electric arc furnaces, the slag composition is optimized not for dephosphorization, but for foaming in the foamed slag process. The phosphorus content [P] of the molten metal immediately before refining is 100 ppm to 1500 ppm. In contrast, the phosphorus content [P] of the poured liquid crude steel is 400 ppm or less.
[0047] As already described, desulfurization may be performed after removing the molten metal from the melting furnace and before filling the converter. For this purpose, in particular, calcium oxide and / or calcium carbide and / or magnesium are added to the molten metal. In this case, the present iron sulfide FeS reacts essentially to obtain calcium sulfite CaS or magnesium sulfite MgS. The formed CaS or MgS then binds in the basic slag.
[0048] The sulfur content [S] of the molten metal immediately before refining (and therefore after any desulfurization) is a maximum of 1500 ppm. The sulfur content [S] of the poured liquid crude steel is similarly a maximum of 1500 ppm.
[0049] The molten metal and the extracted liquid crude steel may contain manganese. In such cases, the manganese content [Mn] of the molten metal immediately before refining is a maximum of 0.5%. In contrast, the manganese content [Mn] of the extracted liquid crude steel is 0.4% or less.
[0050] The molten metal and / or the poured liquid crude steel may contain further unavoidable impurities, totaling up to 2.0%.
[0051] The iron content [Fe] of the molten metal immediately before refining is at least 90.0%. The iron content [Fe] of the poured liquid crude steel is at least 97.0%.
[0052] In a preferred variation, the metal molten material immediately before purification has an elemental content of at least one, preferably more, and especially all of the following trace elements: Carbon [C]: at least 1.0%, especially at least 1.5%, 5.0% or less, especially 4.5% or less. Nitrogen [N]: 450 ppm or less, especially above 50 ppm. Depending on the circumstances, oxygen [O]: 0-50 ppm, Depending on the circumstances, phosphorus [P]: 100-1500 ppm, Depending on the circumstances, sulfur [S]: 0-1500 ppm, Depending on the case, silicon [Si]: 0~1.5%, Depending on the circumstances, manganese [Mn]: 0-0.5%.
[0053] In particular, the molten metal contains the following immediately before purification: Carbon [C]: at least 1.0%, especially at least 1.5%, 5.0% or less, especially 4.5% or less. Nitrogen [N]: 450 ppm or less, especially above 50 ppm. Depending on the circumstances, oxygen [O]: 0-50 ppm, Depending on the circumstances, phosphorus [P]: 100-1500 ppm, Depending on the circumstances, sulfur [S]: 0-1500 ppm, Depending on the case, silicon [Si]: 0~1.5%, Depending on the case, manganese [Mn]: 0~0.5%, The remainder: iron and unavoidable impurities, where the total impurities are less than 2.0%.
[0054] In a preferred modification, the poured liquid crude steel, as a metal molten body immediately before refining, has at least one, preferably more, and especially all, trace elements from the following comparisons: Carbon [C]: 600 ppm or less, especially 500 ppm or less. Nitrogen [N]: 50 ppm or less, especially 30 ppm or less. Oxygen [O]: at least 300 ppm, 2300 ppm or less. Depending on the circumstances, phosphorus [P]: 0-400 ppm, Depending on the circumstances, sulfur [S]: 0-1500 ppm, Depending on the circumstances, silicon [Si]: 0-300 ppm, Depending on the circumstances, manganese [Mn]: 0-0.4%.
[0055] In particular, the poured liquid crude steel contains the following: Carbon [C]: 600 ppm or less, especially 500 ppm or less. Nitrogen [N]: 50 ppm or less, especially 30 ppm or less. Oxygen [O]: at least 300 ppm, 2300 ppm or less. Depending on the circumstances, phosphorus [P]: 0-400 ppm, Depending on the circumstances, sulfur [S]: 0-1500 ppm, Depending on the circumstances, silicon [Si]: 0-300 ppm, Depending on the case, manganese [Mn]: 0~0.4%, The remainder: iron and unavoidable impurities, where the total impurities are less than 2.0%.
[0056] The process of the present invention using a converter has the further advantage that the composition of the molten furnace slag can be freely adjusted, whereas in the case of an electric arc furnace, the slag is generally optimized and therefore cannot be changed as desired.
[0057] Consequently, the composition can be adjusted to be similar to that of foundry sand, for example. Therefore, molten furnace slag can have further applications, for example, in the cement industry, similar to foundry sand.
[0058] In a preferred embodiment, the melting furnace having arc resistance comprises at least one electrode configured as a Soderberg electrode.
[0059] A Soderberg electrode has an outer shell, inside which fins (called guide plates) are positioned. The outer shell is continuously filled with electrode blocks, for example, in the form of briquettes, blocks, or cylinders. As the electrode wears down in the region of the end facing the molten material, the electrode continuously descends during operation and is replenished from above with electrode material. Furthermore, the outer shell is continuously extended by joining additional material.
[0060] In a preferred embodiment, the melting furnace, which has arc resistance, is equipped with exactly three electrodes and operates on three-phase AC.
[0061] In a preferred embodiment, the process includes an upstream direct reduction process for producing directly reduced iron. The assembly in this case comprises a direct reduction plant upstream, preferably immediately upstream, of a melting furnace with arc resistance. In this direct reduction process, a solid-phase reaction occurs in which oxygen is removed from the iron ore. For this purpose, charcoal or natural gas has traditionally been used as a reducing agent. In recent years, hydrogen has also been frequently proposed as a reducing agent. Because this reaction occurs below the melting point of the iron ore, the ore's shape remains unchanged. The removal of oxygen results in a weight reduction of approximately 27-30%, yielding a honeycomb microstructure of the reaction product (solid porous iron with many air-filled gaps). Therefore, directly reduced iron is often also called iron sponge.
[0062] In a preferred embodiment, the direct reduction plant comprises a shaft furnace having a reduction zone through which iron ore passes opposite a reducing gas.
[0063] In a specific modification of the process, the reduction zone is located above the cooling zone within the shaft furnace. The iron ore then passes through the shaft furnace vertically from top to bottom. Such a shaft furnace, due to the underlying chimney effect, allows for good flow of cooling gas through the iron ore and reducing gas. In particular, the reducing gas flows through the reduction zone opposite to the direction of movement of the iron ore. Correspondingly, the cooling gas also flows through the cooling zone opposite to the direction of movement of the manufactured iron sponge. Thus, in both the cooling and reduction zones, a counterflow method is used to achieve efficient reactions between gas and solid.
[0064] The reducing gas used is, in particular, CO or H2, or a mixture containing CO and H2. The reduction reaction here is as follows ("(s)" indicates a solid; curly braces indicate a gaseous substance): 3Fe2O3(s)+{CO}=2Fe3O4(s)+{CO2} Fe3O4(s)+{CO}=3FeO(s)+{CO2} FeO(s) + {CO} = Fe(s) + {CO2} 3Fe2O3(s)+{H2}=2Fe3O4(s)+{H2O} Fe3O4(s) + {H2} = 3FeO(s) + {H2O} FeO(s) + {H2} = Fe(s) + {H2O} Reducing gases are typically produced from fossil hydrocarbons (e.g., natural gas or coking furnace gas). As an example, the reaction is described below using methane as the starting material. Other hydrocarbons can also be used as starting materials.
[0065] In the first modified implementation, the reducing gas is produced in a gas reformer from methane, CO2, and steam (MIDREX® process).
[0066] CH4 + CO2 = 2CO + 2H2 CH4 + H2O = CO + 3H2 As a result, a gas circuit is obtained in which fresh methane is mixed with purified off-gas from the shaft furnace upstream of the gas reformer. The off-gas from the shaft furnace contains CO2 and vapor as products of the reduction reaction. Utilizing the catalytic reaction within the gas reformer, a reducing gas containing H2 and CO is produced from methane, CO2, and vapor. This reducing gas is supplied to the shaft furnace, where it reduces the iron ore according to the reaction equation described above. The reaction products formed are CO2, vapor, and iron sponge. The CO2 and vapor, as well as any unused reducing gas, are mixed with methane and returned to the gas reformer.
[0067] In the alternative implementation variation (HYL® process), the reducing gas is, It is produced by a catalytic reaction when methane is mixed with vapor, the mixture is heated, and then passed over a catalyst.
[0068] The CH4+H2O=CO+3H2 catalyst may be, for example, nickel present in the iron-nickel pipe that leads the gas to the shaft furnace. In a specific configuration of this process, the high-temperature iron sponge itself acts as a catalyst at the bottom of the reduction zone. At the same time, carbon is deposited on the iron sponge, thereby increasing the carbon content of the iron sponge.
[0069] Alternatively, the reducing gas used may be hydrogen, which can be produced regardless of climate, particularly by electrolysis. In that case, the process further includes the following steps: • A process that uses electrolytically produced hydrogen to directly manufacture reduced iron from iron ore in a shaft furnace.
[0070] The use of electrolyzed hydrogen improves the carbon footprint of processes by reducing CO2 emissions and the consumption of fossil energy carriers.
[0071] This hydrogen can either completely replace natural gas as a starting material or be partially added to the above process to reduce natural gas consumption. As the hydrogen content increases, the reduction moves further into the defined reaction equation with H2, thus deviating from the three reaction equations with CO.
[0072] In a preferred development of the process, the direct reduction process includes a carbonization step in which the produced directly reduced iron is brought into contact with a carbon-containing gas to deposit carbon onto the produced iron. The carbon-containing gas used may be, in particular, natural gas or CO2. In this carbonization reaction, various chemical reaction mechanisms arise depending on the gas used. The carbon-containing gas is preferably introduced into the cooling zone of the shaft furnace to simultaneously cool and carbonize the produced directly reduced iron. Furthermore, the high-temperature directly reduced iron in the cooling zone can further act as a catalyst for the carbonization reaction. The carbonization step increases the carbon content of the directly reduced iron and, consequently, the carbon content of the metal molten in the downstream melting furnace. This brings two advantages: firstly, the melting point of the directly reduced iron is lowered, thereby reducing energy consumption in the melting furnace; and secondly, as already described, an increased carbon content is favorable to the denitrification mechanism described in the downstream converter.
[0073] The present invention further relates to a process for manufacturing ULC steel, particularly IF steel, preferably non-directional electromagnetic strips, comprising the following steps: • The process for producing low-nitrogen crude steel through the above process, • Secondary metallurgical treatment of manufactured crude steel, • The process of casting crude steel in a continuous casting plant.
[0074] This process has the same advantages as the above process for producing low-nitrogen crude steel.
[0075] Secondary metallurgical treatment of manufactured crude steel includes, in particular, vacuum treatment.
[0076] In vacuum processing, the carbon content [C] of the manufactured crude steel, which is 600 ppm or less, is reduced to 150 ppm or less, preferably 100 ppm or less, preferably 50 ppm or less, and especially to 30 ppm or less, the desired maximum content for ULC steel grades. Vacuum processing is particularly effective when utilizing the Ruhrstahl-Heraeus process. Alternatively, vacuum processing can be carried out using ladle tank degassing.
[0077] The present invention further relates to an assembly for carrying out the above process. The assembly comprises a melting furnace having arc resistance for producing a metal molten body, having a converter downstream, preferably immediately downstream, for refining the metal molten body to obtain liquid crude steel.
[0078] This assembly has the advantages described above regarding the process.
[0079] In preferred embodiments, the assembly comprises a direct reduction plant upstream, preferably immediately upstream, of the melting furnace having arc-resistant heating, and / or a secondary metallurgical plant downstream, preferably immediately downstream, of the converter. Connecting the direct reduction plant directly to the melting furnace has the advantage that the melting furnace can be filled with the produced direct-reduced iron while it is still hot. This reduces the energy input in the melting operation. Equally advantageous is connecting the secondary metallurgical plant directly to the converter, as this allows the liquid crude steel to be directly fed into further processing.
[0080] The present invention also relates to an assembly for carrying out the above-described process for producing ULC steel. The assembly comprises a melting furnace having arc-resistant properties for producing a metal molten body, having a downstream converter for refining the metal molten body to obtain liquid crude steel; a secondary metallurgical plant downstream of the converter; and a continuous casting plant downstream of the secondary metallurgical plant. The secondary metallurgical plant is particularly designed as a vacuum degassing plant, preferably an RH plant.
[0081] The present invention further relates to the modification of an existing assembly for producing low-nitrogen crude steel, having a blast furnace and an existing converter downstream of the blast furnace, by adding a melting furnace with arc resistance upstream of the existing converter, preferably immediately upstream, and dismantling the existing blast furnace. Surprisingly, it has been found that low-nitrogen crude steel can be produced with a significant reduction in CO2 emissions by using a melting furnace with arc resistance upstream of the existing converter, rather than the existing blast furnace. Such a melting furnace has never been coupled to a separate converter to produce a specific steel grade. Only separate converters combined with blast furnaces have been known to date. According to the present invention, it is recognized that the blast furnace can be replaced with a simple melting furnace with arc resistance as described. This combination results in the synergistic effects described with respect to the process. One of these is, in particular, that the nitrogen content of the crude steel produced is particularly low. Furthermore, this modification can be carried out at a relatively low cost because the existing converter can still be used. Due to the low nitrogen content, it is equally possible to continue using the further downstream secondary metallurgical plant in the same manner. This has the advantage that recertification of the steel grade production process for the end customer is not required. Since the certification of the manufacturing process relates only to the process steps downstream of the converter, it is possible to avoid recertification if these steps remain unchanged. The modifications of the present invention enable the adoption of these steps entirely without changing the blast furnace process.
[0082] The present invention further relates to the modification of an existing assembly for producing ULC steel grades, comprising a blast furnace, an existing converter downstream of the blast furnace, and a secondary metallurgical plant downstream of the converter. The process includes the addition of a melting furnace having arc-resistant heating upstream of the existing converter, preferably immediately upstream, and the dismantling of the existing blast furnace. Since low nitrogen crude steel is used as the starting material for producing ULC steel grades, this process of modifying an existing assembly for producing ULC steel grades has the same advantages as the above process of modifying an existing assembly for producing low nitrogen crude steel.
[0083] In preferred modifications, the two aforementioned modification processes include the addition of a direct reduction plant upstream, preferably immediately upstream, of the melting furnace, which has arc-resistant properties. Connecting the direct reduction plant directly to the melting furnace has the advantage that the melting furnace can be filled with the produced direct-reduced iron while it is still hot. This reduces energy consumption in the melting operation.
[0084] The present invention will be described in more detail by the drawings. The drawings are as follows: [Brief explanation of the drawing]
[0085] [Figure 1] Flowchart of the process of the present invention for the production of crude steel [Figure 2] Schematic diagram of a melting furnace with arc resistance. [Figure 3] Schematic diagram of a converter [Figure 4] Schematic diagram of a direct reduction plant [Modes for carrying out the invention]
[0086] Figure 1 shows a flow diagram of the process of the present invention for the production of low nitrogen crude steel. In the first optional step, reduced iron is produced directly from iron ore in a shaft furnace. Alternatively, the directly reduced iron may be purchased. In the next step, the directly reduced iron is introduced into a melting furnace having arc-resistant heating. Furthermore, scrap may also be introduced into the melting furnace. In the melting furnace, the iron and / or scrap are melted to obtain a molten metal and slag. Subsequently, the molten metal is removed from the melting furnace and used to fill a converter. In the converter, the molten metal is refined to obtain liquid crude steel. Subsequently, the liquid crude steel is tapped in the converter.
[0087] Figure 2 shows a melting furnace 13 with arc resistance in the form of a buried electric arc furnace (SAF). The melting furnace 13 comprises a furnace vessel 15 lined on the inside with refractory material 17. Three AC-operated electrodes 21 protrude into the interior 19. The molten metal 23 is already inside the interior 19. A layer of slag 25 has settled on top of the molten metal 23. The three electrodes 21 protrude into the slag 25. Thus, an electric current is formed between the electrodes 21, which passes through the slag layer 25 and heats the slag layer 25 by resistance heating. This heating is transferred from the slag layer 25 to the molten metal 23. The interior 19 is terminated at the top by a lid 29, through which the three electrodes 21 protrude. The electrodes 21 are designed as Soderberg electrodes.
[0088] Figure 3 shows a converter 31. The converter 31 comprises a converter vessel 33 having a refractory lining 35. A molten metal 37 is contained within the converter vessel 33. Oxygen can be blown onto the surface of the molten metal 37 using a probe 39 that protrudes into the converter vessel 33 from the top. The converter 41 is closed at the top by a lid 38 through which the probe 39 is guided. The converter base 41 has a nozzle 43 through which an inert gas can be blown into the converter 31. The converter 31 has a lateral tap orifice 45 through which the liquid crude steel can be removed by tilting the converter vessel 33 after refining.
[0089] Figure 4 shows a schematic diagram of the direct reduction plant 51. The direct reduction plant 51 includes a shaft furnace 53. The shaft furnace 53 has a reduction zone 55 and a cooling zone 57. The reduction zone 55 is located above the cooling zone 57. Iron ore is filled into the shaft furnace 53 from the top. At the bottom of the shaft furnace 53, the produced direct reduced iron can be removed. At the same time, reducing gas enters the shaft furnace 53 through the inlet 59. The reducing gas then flows through the iron ore in the reduction zone 55. The unused reducing gas then exits again at the outlet 61 along with some gaseous reaction products. Thus, the reducing gas flows through the reduction zone 55 opposite to the direction of movement of the iron ore. After leaving the reduction zone 55, the direct reduced iron enters the cooling zone 57. In the cooling zone 57, the cooling gas flows through the iron sponge opposite to the direction of movement of the iron. For this purpose, the cooling gas enters the shaft furnace 53 through the inlet 63. Unused cooling gas is released again at outlet 65 along with some gaseous reaction products. Needless to say, a certain proportion of the cooling gas may enter the reduction zone 55. Similarly, a certain proportion of the reducing gas may enter the cooling zone 57. The cooling gas preferably contains carbon in order to carbonize the directly reduced iron produced.
Claims
1. The following are the process steps: - A step of obtaining a metal molten body (23) and slag (25) by directly melting reduced iron and / or scrap in an arc resistance heating melting furnace (13) using a reducing atmosphere, wherein the iron content (Fe) of the slag (25) in the melting furnace (13) is less than 20% by weight, and the arc resistance heating melting furnace (13) is of the Submerged Electric Arc Furnace type or the Open Slag Bath Furnace type. - A step of removing the molten metal (23) from the melting furnace (13) and using it to fill the converter (31), A process for producing low-nitrogen crude steel, comprising the steps of: purifying the molten metal body (37) in the converter (31) to obtain liquid crude steel; and tapping the liquid crude steel having a nitrogen content [N] of 50 ppm or less, wherein if the nitrogen content [N] of the molten metal body (37) exceeds 50 ppm, the nitrogen content [N] is reduced; or if the nitrogen content [N] of the molten metal body (37) is less than 50 ppm, the nitrogen content [N] is kept low or further reduced; The process is characterized in that the molten metal (37) has at least 20 carbon-to-nitrogen content ratio [C] / [N] immediately before the purification.
2. The process according to claim 1, characterized in that the carbon content [C] of the molten metal increases within the melting furnace (13).
3. The process according to claim 1 or 2, characterized in that the carbon content [C] of the molten metal increases within the converter (31).
4. The process according to any one of claims 1 to 3, characterized in that the molten metal (37) has the following trace element content immediately before the purification: Carbon [C]: at least 1.0%, 5.0% or less. Nitrogen [N]: 450 ppm or less, Depending on the circumstances, oxygen [O]: 0-50 ppm, Depending on the circumstances, phosphorus [P]: 100-1500 ppm, Depending on the circumstances, sulfur [S]: 0 to 1500 ppm, Depending on the case, silicon [Si]: 0-1.5%, Depending on the circumstances, manganese [Mn]: 0-0.5%.
5. The process according to any one of claims 1 to 4, characterized in that the poured liquid crude steel has the following trace element content: Carbon [C]: 600 ppm or less, Nitrogen [N]: 50 ppm or less, Oxygen [O]: at least 300 ppm, 2300 ppm or less. Depending on the circumstances, phosphorus [P]: 0-400 ppm, Depending on the circumstances, sulfur [S]: 0 to 1500 ppm, Depending on the case, silicon [Si]: 0 to 300 ppm, Depending on the circumstances, manganese [Mn]: 0-0.4%.
6. The process according to any one of claims 1 to 5, wherein the purification involves blowing oxygen onto the molten metal (37) using a retractable water-cooled probe, the blowing time being at least 10 minutes.
7. The process according to claim 6, characterized in that argon is blown in through a nozzle (43) in the converter base (41).
8. The process according to any one of claims 1 to 7, including the following prior steps: - A process for directly producing reduced iron from iron ore in a shaft furnace (53) with the consumption of electrolytically produced hydrogen, or natural gas, or coking furnace gas.
9. The process for manufacturing ULC steel includes the following steps: - A step of producing low-nitrogen crude steel by the process described in any one of claims 1 to 8, - Secondary metallurgical treatment of the manufactured crude steel, - A process of casting the crude steel in a continuous casting plant.
Citation Information
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