Method for conditioning electric furnace slags

Abstract

The invention relates to a method for conditioning electric furnace slags (1) which are treated in the molten state with a carbon-containing reducing agent, wherein a hydrogen-containing forming gas is introduced into the molten electric furnace slag (1).

Description

[0001] Methods for conditioning electric arc furnace slag

[0002] The invention relates to a method for conditioning electric arc furnace slag.

[0003] Iron oxide-rich slags typically arise from industrial melting and refining processes, such as the oxygen blowing process or the melting of scrap metal and / or (directly) reduced iron carriers in smelting furnaces. The resulting slags have iron oxide contents exceeding 10 wt.%. Electric arc furnace slags, also known as EOS, are particularly rich in iron oxide and therefore have limited reusability and / or recyclability.

[0004] Iron oxide-rich slags therefore have only limited applications in the construction industry or landfill construction, making high-quality recycling on a large scale virtually impossible. Subsequent reduction of these iron oxide-rich slags with carbon is suboptimal, as this process requires additional time and energy. Furthermore, when using solid carbon, residues may remain in the slag. Introducing carbon into slags is a known method; see also Chapter 2.8.1 in Gara et al. “TREATMENT OF RESIDUES AND WASTE IN THE IRON AND STEEL INDUSTRY”, MONOGRAPHS Volume 92 M-092, Vienna, 1998, available at the following link: https: / / www.umweltbundesamt.at / fileadmin / site / publikationen / M092.pdf, with the main aim of causing them to foam in order to trigger a reverse reaction of the iron oxide formed in the slag and to reduce energy consumption and noise emissions.As can be seen from Table 2.8-2 of the aforementioned publication, the oxide iron contents in the electric arc furnace slag are nevertheless very high at 10 wt.% and more, and therefore not suitable for a wide range of applications.

[0005] BR 9 902 397 A deals with the granulation and comminution of slag, whereby water and carbon are used to convert it into CO + H2, and this gas mixture (fission gas) can then be used for direct reduction and propellant gas production. The teaching relates to the production of a hydrogen-containing gas from the granulation of slag.

[0006] EP 0 292 992 Bl discloses a process for recovering non-ferrous metals from slags. Hydrogen is listed only as one of the possible gases for reduction. The objective is to provide a process for conditioning electric arc furnace slags, which can improve the quality and / or further processing of these slags.

[0007] The problem is solved by a method according to claim 1. Further advantageous embodiments are described in the dependent claims.

[0008] The teaching of the invention relates to a method for conditioning electric arc furnace slags which are treated in the molten state with a carbon-containing reducing agent, wherein a hydrogen-containing forming gas is introduced into the molten electric arc furnace slag.

[0009] The production of iron melts and slag in an electric arc furnace is state of the art. This process essentially involves introducing iron carriers, comprising at least one of the following components: sponge iron, scrap, pig iron, and / or iron-containing metallurgical residues and / or recycled metallurgical materials; slag formers, comprising or consisting of at least one component from the group SiO₂, CaO, MgO, or Al₂O₃; and optionally, carbon-containing reducing agents, such as coal, coke, and / or non-fossil carbons. These materials are then melted to produce an iron melt and a layer of molten electric arc furnace slag. The electric arc furnace has several electrodes that can be, or are, supplied with an electric current, thus providing the energy required for melting. Depending on the size of the electric arc furnace, three, four, five, six, or more than six electrodes can be used.The energy required for melting is preferably supplied at least partially from renewable energy sources (solar, wind, water, biomass). If the required energy can be supplied entirely from renewable sources, and if it is available in the required quantity, the electric arc furnace can be operated in a climate-neutral (or more climate-neutral) manner. Conventionally produced electric arc furnace slags have a total content (in wt.%) of oxide iron of at least 10%, in particular at least 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, and a maximum of 50%, in particular a maximum of 45%, preferably a maximum of 40%. The oxide iron is combined with Fe. x O yThis refers to FeO, Fe₂O₃, Fe₃O₄, or a mixture thereof. In most cases, the iron oxide in electric arc furnace slag consists essentially of FeO. The invention therefore relates to the presence of molten electric arc furnace slag and its conditioning, followed by improved quality and / or further processing.

[0010] The electric furnace can be an OSBF (Open Slag Bath Furnace) type furnace. This includes electric reduction furnaces, especially SAFs (Submerged Electric Arc Furnaces), which are melting furnaces with arc resistance heating. These furnaces generate electric arcs between the electrode and the feedstock and / or the liquid phase, or they heat the feedstock and / or the liquid phase using the Joule effect. In SAFs, the electrodes are immersed in the feedstock and / or the liquid phase, particularly in the liquid slag. Depending on the operating principle, electric reduction furnaces can be designed as alternating current arc reduction furnaces (SAFac) or direct current arc reduction furnaces (SAFdc). Alternatively, melting furnaces with direct arc action, which differ from the operating principle described above, so-called EAFs (Electric Arc Furnaces), can also be used. These furnaces generate electric arcs between the electrode and the liquid phase.This includes the alternating current arc furnace (EAFac), the direct current arc furnace (EAFdc) and the ladle furnace (LF).

[0011] For example, electric reduction furnaces with arc resistance heating (SAF) are operated with a reducing atmosphere, whereas electric furnaces with direct arc heating (EAF) are operated with an oxidizing atmosphere.

[0012] According to one embodiment, the forming gas contains or consists of 0.1 to 20 vol% hydrogen, the remainder being nitrogen and / or argon. The hydrogen in the forming gas serves as a reaction accelerator for reducing the iron oxide, particularly in conjunction with a carbon-containing reducing agent. The hydrogen may be present in the forming gas at a concentration of at least 0.3 vol%, preferably at least 0.55 vol%, more preferably at least 0.8 vol%, and most preferably at least 1.15 vol%. The hydrogen may be present in the forming gas at a concentration of up to 17 vol%, preferably at a concentration of up to 13 vol%, more preferably at a concentration of up to 10 vol%, and most preferably at a concentration of up to 7 vol%, for example, to keep the hydrogen content below the explosive limit. The remainder is preferably a protective gas, with nitrogen being the preferred choice due to its lower cost compared to other protective gases.Alternatively or additionally, the use of one or more noble gases, such as argon, is also possible. According to one embodiment, the conditioning of the molten electric arc furnace slag can take place within the electric arc furnace itself. This method has the advantage that no additional equipment is required to adjust the final properties of the molten electric arc furnace slag.

[0013] Molten electric arc furnace slag is produced in an electric arc furnace and transferred to a ladle. According to an alternative design, the conditioning of the molten electric arc furnace slag can then take place in the ladle. This method allows for better and / or more targeted control over the final properties, as, unlike conditioning in the electric arc furnace, there is no (negative) impact on the molten iron. In particular, the conditioning time (treatment time) can be individually adjusted as needed.

[0014] According to one embodiment, the forming gas can be introduced into the molten electric arc furnace slag together with the carbon-containing reducing agent. Together with the hydrogen contained in the forming gas, the reaction for reducing the iron oxide can be accelerated, which can have a positive effect on the conditioning time (treatment time). Preferably, the forming gas can act as a carrier gas for the carbon-containing reducing agent, particularly if the carbon-containing reducing agent is in solid form, preferably as particles, to further facilitate the transport of the carbon-containing reducing agent into the molten electric arc furnace slag.

[0015] According to an alternative design, the forming gas can be introduced separately from the carbon-containing reducing agent. This has the advantage of allowing the gas to be dosed as needed, depending on the final properties to be achieved.

[0016] Carbon-containing reducing agents can preferably be introduced in solid form and may contain or consist of, for example, waste plastics, biomass, plastics or mixtures thereof.

[0017] Carbon-containing reducing agents can also be introduced in gaseous form and may, for example, contain or consist of carbon monoxide. After conditioning, the total content of oxide iron in the electric arc furnace slag is a maximum of 10.0 wt.%. The total content (in wt.%) of oxide iron can be, in particular, a maximum of 9.5%, 9.0%, 8.5%, preferably a maximum of 8.0%, 7.5%, 7.0%, preferably a maximum of 6.5%, 6.0%, 5.5%, especially preferably a maximum of 5.0%, 4.5%, 4.0%, further preferably a maximum of 3.5%, 3.0%, 2.5%, and more preferably a maximum of 2.0%, 1.5%, 1.0%. Theoretically, a total content of 0% would be possible, but this is not practically relevant, as the total content of oxide iron will generally always be > 0%, and in particular > 0.25%.

[0018] To not only reduce the iron content of electric arc furnace slag but also, if necessary, to convert it to a desired target composition, the slag former is added in an amount sufficient to achieve a basicity B4 between 0.7 and 4.5. B4 can be at least 0.8, preferably at least 0.9, and particularly at most 3.7, preferably at most 2.6, and preferably 1.8. The basicity B4 corresponds to the ratio (CaO + MgO) to (SiO2 + Al2O3), the determination of which characteristic values ​​is generally familiar to those skilled in the art in solid-state slag.

[0019] The composition of electric arc furnace slag can be determined, for example, according to DIN EN ISO 12677:2013-02 “Chemical analysis of refractory products using X-ray fluorescence (XRF) - Fused Cast-Bead method”.

[0020] According to one embodiment, the electric arc furnace slag, or parts thereof, can be granulated after conditioning and, by rapid cooling, such as by wet or dry granulation according to the prior art, transformed into an amorphous structure with a given chemical composition. This means that through granulation, it acquires a glass content of at least 40%, particularly at least 70%, preferably at least 90%, and at most 100%, particularly up to 99%. Thus, it is then referred to as granulated electric arc furnace slag. The glass content can be determined by X-ray diffraction analysis, see DIN EN 13925-1:2003-07, "Non-destructive testing - X-ray diffractometry of polycrystalline and amorphous materials" - Part 1: General principles. This structure is more reactive than a crystalline structure, which forms upon slow cooling. In granular form, this product can then, at best, be used as a cement clinker substitute.It has latent hydraulic properties, meaning it reacts upon the addition of water. This would not occur in a product with a crystalline structure, as the structure is too stable, whereas the amorphous structure is not. Through the preferred combination of conditioning and granulation, a blast furnace slag-like product can be created.

[0021] An example of the composition of electric arc furnace slag after conditioning and optional granulation is the following composition in wt.%: CaO: 30 to 60%, SiO2: 25 to 50%, Al2O3: 4 to 18%, MgO: 3 to 15%, Fe x O y : > 0, in particular > 0.10 to 5% and impurities totaling 100% by weight.

[0022] Due to the dependence on specific circumstances, such as particular plant parameters, the person skilled in the art carrying out the process must empirically adjust the concentration of a forming gas to be introduced and the conditioning time in the electric arc furnace or ladle so that the conditioned electric arc furnace slag exhibits the desired state. This empirical determination of a sufficiently high concentration of hydrogen-containing forming gas and / or a sufficiently long conditioning time does not pose any particular difficulties for the person skilled in the art, as it involves less technical than economic considerations.

[0023] The invention will now be explained in more detail using exemplary embodiments.

[0024] Figure 1 shows an exemplary embodiment of an electric furnace 10 into which iron supports, slag formers, and optionally carbon-containing reducing agents are introduced to melt these substances into a molten iron (2) and a molten electric furnace slag (1) above it. The electric furnace (10) has several electrodes (11) which can be supplied with electric current and thus provide the energy required for melting. The operating principle of an electric furnace (10) for melting is known to those skilled in the art. The electric furnace (10) can preferably be an electric arc furnace (EAF).

[0025] A method for conditioning electric arc furnace slag (1) involves treating the molten slag with a carbon-containing reducing agent while it is still molten, with the introduction of a hydrogen-containing forming gas into the molten electric arc furnace slag. The forming gas can be introduced directly into the molten electric arc furnace slag (1), for example, by means of lances (12). The forming gas contains or consists of 0.1 to 20 vol% hydrogen, with the remainder being nitrogen and / or argon. In this exemplary embodiment, the conditioning of the molten electric arc furnace slag (1) takes place in the electric arc furnace (10). The forming gas is preferably introduced into the molten electric arc furnace slag (1) together with the carbon-containing reducing agent, with the forming gas acting as a carrier gas for the carbon-containing reducing agent.

[0026] Figure 2 shows an alternative exemplary embodiment of an electric arc furnace 10 in which, as in Figure 1, a molten iron (2) and a molten electric arc furnace slag (1) above it are melted. Unlike in Figure 1, the molten electric arc furnace slag (1) in the electric arc furnace (10) is transferred to a ladle (20), and the conditioning of the molten electric arc furnace slag (1) takes place in the ladle (20). The forming gas can, for example, be introduced directly into the molten electric arc furnace slag (1) in the ladle (20) by means of lances (22). The forming gas contains or consists of 0.1 to 20 vol.% hydrogen, the remainder being nitrogen and / or argon. The forming gas is preferably introduced into the molten electric arc furnace slag (1) together with the carbon-containing reducing agent, the forming gas acting as a carrier gas for the carbon-containing reducing agent.

[0027] The electric arc furnace slag to be conditioned has a total oxide iron content of at least 10 wt.%, wherein the oxide iron may be in the form of FeO, Fe₂O₃, Fe₃O₄, or a mixture thereof. After conditioning, the electric arc furnace slag (1) may contain a total oxide iron content of up to 10.0 wt.%. After conditioning, the electric arc furnace slag (1) may preferably have a basicity B₄ between 0.7 and 1.8.

[0028] On a laboratory scale, an electric arc furnace slag (1) was melted in an EAF-type electric arc furnace (10) according to the principle shown in Figure 2 and transferred to a ladle (20) for conditioning. The composition of the electric arc furnace slag (1) to be conditioned was (all values ​​in wt.%): 40.1% CaO, 14.1% SiO₂, 5.67% Al₂O₃, 11.7% MgO, 22.7% Fe x O y The basicity B4 was 2.62.

[0029] 25% SiO₂ and 10% Al₂O₃ were added as slag formers, based on the total amount of electric arc furnace slag (1). A forming gas containing 5% hydrogen by volume and nitrogen as the remainder, carrying carbon particles, was also supplied. The conditioning time was approximately 20 minutes. After conditioning, the electric arc furnace slag (1) had the following composition (all values ​​in wt%): 36.7% CaO, 35.8% SiO₂, 14.4% Al₂O₃, 10.7% MgO, <2% Fe x O y , < 1% Fe meThe basicity B4 was 0.95. With a total iron oxide content of less than 2 wt% and a basicity B4 of 0.95, the conditioned electric arc furnace slag was very similar to granulated blast furnace slag. Subsequently, the conditioned electric arc furnace slag (1) with a glass content of > 90% was granulated using a known dry process. The invention allows the quality of electric arc furnace slags to be improved and / or increased, thus enabling previously inaccessible applications for this type of slag. Preferably, the electric arc furnace slags can be used as a feedstock in the cement industry, for example, like the granulated blast furnace slag (blast furnace slag) currently used as standard in blast furnaces.

Claims

Patent claims 1. A method for conditioning electric arc furnace slag (1) which is treated in the molten state with a carbon-containing reducing agent, characterized in that a hydrogen-containing forming gas is introduced into the molten electric arc furnace slag (1).

2. The method according to claim 1, wherein the forming gas contains or consists of between 0.1 and 20 vol% hydrogen, the remainder being nitrogen and / or argon.

3. Method according to one of the preceding claims, wherein the conditioning of the molten electric furnace slag (1) takes place in the electric furnace (10).

4. Method according to claim 1 or 2, wherein the molten electric furnace slag (1) is produced in an electric furnace (10), which is transferred to a ladle (20) and the conditioning of the molten electric furnace slag (1) takes place in the ladle (20).

5. Method according to one of the preceding claims, wherein the forming gas is introduced into the molten electric arc furnace slag (1) together with the carbon-containing reducing agent.

6. The method according to claim 5, wherein the forming gas acts as a carrier gas for the carbon-containing reducing agent.

7. Method according to any one of claims 1 to 4, wherein the forming gas is introduced separately to the carbon-containing reducing agent.

8. Method according to any of the preceding claims, wherein the carbon-containing reducing agent is introduced in the solid state and contains or consists of waste plastics, biomass, plastics or mixtures thereof.

9. A method according to any of the preceding claims, wherein the carbon-containing reducing agent is introduced in a gaseous state and contains or consists of carbon monoxide.

10. Method according to any of the preceding claims, wherein the electric arc furnace slag (1) after conditioning comprises a total content of oxide iron of a maximum of 10.0 wt.%.

11. Method according to one of the preceding claims, wherein the electric furnace slag (1) after conditioning has a basicity B4 between 0.7 and 4.5, wherein basicity B4 corresponds to the ratio CaO + MgO to SiO2+ Al2O3.

12. Method according to one of the preceding claims, wherein the electric arc furnace slag (1) or parts thereof is granulated after conditioning and has a glass content of at least 40%.

13. A method according to any of the preceding claims, wherein the electric arc furnace slag (1) consists of the following components in wt.%: CaO: 30 to 60%, SiO2: 25 to 50%, Al2O3: 4 to 18%, MgO: 3 to 15%, Fe x O y : > 0 to 5% and impurities totaling 100% by weight.

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