The present disclosure relates to the field of electric arc furnaces for chemical and/or metallurgical applications, such as melting and/or treating metals and/or metallic wastes and/or by-products containing metals and other chemical compounds, such as metal oxides.
A wide variety of furnaces whose geometry, procedure and heating systems differ significantly are used in different chemical and metallurgical applications. Depending on their mode of operation, the furnaces can be grouped into continuous or batch furnaces, which can use electricity or fossil fuels. They may also be classified according to their geometry. They can be of direct or indirect application. The advantages of each type of furnace depend on several factors, such as the type and size of the load used, since load determines the energetic efficiency and metallurgical quality resulting from the applied process, such as melting or treatment process.
A well-known type of furnace using electricity is the direct current (DC) electric arc furnace. An example of DC electric arc furnace is disclosed in U.S. Pat. No. 4,466,824. The furnace has a crucible for collecting molten material. The surface of the crucible conceived to be in contact with molten material is made of refractory material. An anode is mounted at the bottom section of the crucible. A cover is disposed on the top section of the furnace. A cathode is inserted into the furnace through a central opening made on the cover. In operation of the furnace, when the cathode tip is in close proximity to the molten material filling the crucible, a plasma arc is started.
In other DC arc furnaces, the anode is built in the crucible in the form of different kind of electrical conductors inserted within the refractory material of which the crucible is made. This is disclosed, for example, in U.S. Pat. Nos. 4,541,099, 5,381,440 and 5,381,441.
However, in the cited disclosures there are local electric connection areas which can have poor conductivity when starting operation with charges being at low temperature (for example <750° C. for ferrous charges or <450° C. for copper non-ferrous charges) or even at room temperature from cold furnace start. Poor conductivity in the electric circuit can generate huge energy losses and even malfunctioning of the facility. In the same way, this kind of local connections can lose completely electric conductivity due to cavities formed in the charge during melting or charging of the furnace.
The present disclosure provides an improved electric arc furnace for chemical and/or metallurgical applications, such as melting and/or treating metals and/or metallic wastes and/or by-products containing metals and other chemical compounds, such as metal oxides, either simple or complex metal oxides.
The furnace of the disclosure comprises a chamber delimited by a crucible. The chamber has the double function of receiving the material to be treated and heating it for its treatment. The furnace is heated by an electric system, such as a plasma torch electric system, having two electrodes—cathode and anode. The electric system is equipped with a DC power supply. In operation of the furnace, the electrodes allow the current to flow from one electrode to the other one. The anode of the plasma system is the surface delimiting the chamber, that is to say, the crucible of the furnace. The cathode is an electrode, preferably a graphite electrode, disposed in the upper part of the chamber. The cathode is movable vertically, towards the chamber containing the material to be heated. Cathode and anode are electrically isolated from each other. In operation, when the cathode tip is in close proximity to the molten material filling the crucible, that is to say, the anode, a plasma arc is started. The main body of the furnace is made of one or more refractory materials surrounding the crucible.
According to a first aspect of the present disclosure, there is provided a direct current plasma arc furnace for melting and/or treating a material by production of electric arcs and providing a molten product. The furnace comprises: a tank comprising a crucible delimiting a chamber configured to receive material to be melted and/or treated, a plurality of refractory walls surrounding the outer surface of the crucible and a metallic frame covering the refractory walls; and a heating system configured for heating the received material, the heating system comprising a first electrode acting as cathode and a second electrode acting as anode, wherein the first electrode acting as cathode is a movable electrode configured to project vertically into the chamber delimited by the crucible. The crucible is made of a material comprising at least 98% of synthetic graphite, the crucible being part of an anode system also comprising said second electrode and at least one part connecting the crucible and the second electrode, said crucible having a double function: receiving and holding material to be melted and/or treated and providing electric conduction for the flow of current to heat said material, in such a way that, in use of the furnace, the voltage potential difference between the cathode and any point of the surface of the crucible defined to be in contact with the material to be melted and/or treated is the same.
In embodiments of the disclosure, the heating system comprises a plasma torch.
In embodiments of the disclosure, the cathode is made of a material comprising at least 98% of synthetic graphite.
In embodiments of the disclosure, the at least one part of the anode system comprises: a first elongated portion having a first end connected to the bottom wall of the crucible and extending radially therefrom; and a second elongated portion having a first end connected to the second end of the first elongated portion, the second elongated portion extending vertically until its second end shows up outside the furnace.
In embodiments of the disclosure, the plurality of refractory walls disposed between the outer surface of the crucible and the metallic frame comprises: a first layer of refractory material vertically surrounding the perimeter wall of the crucible; a second layer of refractory material vertically surrounding the first layer; a third layer of refractory material disposed beneath the bottom portion of the crucible; and a fourth layer of refractory material vertically surrounding the second layer and in contact with the outer metallic frame.
The first layer preferably comprises alumina-based corundum. More preferably, it is made of self-sintering alumina-based corundum having an amount of alumina larger than >85%.
The second layer preferably comprises alumina-based concrete. More preferably, it is made of alumina-based conformed concrete having an amount of alumina larger than 90%.
The third layer and the fourth layer preferably comprise calcined bauxite. More preferably, they also comprise alumina-based concrete.
In embodiments of the disclosure, the fourth layer extends downwards with respect to the third layer, surrounding previous refractory portions disposed around the crucible.
In embodiments of the disclosure, the furnace further comprises a fifth layer of refractory material surrounding the second elongated portion of the anode system, the fifth layer being a silica-based self-sintering refractory.
In another aspect of the disclosure, the use of the furnace previously described, is provided, for melting or treating metals and/or metallic wastes and/or by-products containing metals and other chemical compounds.
Thanks to its design and geometry, the proposed furnace is highly efficient and has low energetic consumption and high metallurgic performance. In addition, the furnace is versatile as it can be used for melting/treating different kinds of materials.
Additional advantages and features of the disclosure will become apparent from the detail description that follows and will be particularly pointed out in the appended claims.
To complete the description and in order to provide for a better understanding of the disclosure, a set of drawings is provided. Said drawings form an integral part of the description and illustrate an embodiment of the disclosure, which should not be interpreted as restricting the scope of the disclosure, but just as an example of how the disclosure can be carried out. The drawings comprise the following figures:
The following description is not to be taken in a limiting sense but is given solely for the purpose of describing the broad principles of the disclosure. Next embodiments of the disclosure will be described by way of example, with reference to the above-mentioned drawings showing apparatuses and results according to the disclosure.
In reference to the figures, a possible embodiment of the furnace of this disclosure is described below. The furnace is a melting furnace, meaning that it processes material in melted state. The resulting product after the treatment applied in the furnace is in liquid state. The furnace of the disclosure is based on the direct heating of the loaded material by means of a direct current (DC) plasma arc, also referred to as DC plasma jet, obtained from two electrodes. In particular, furnace 1 is heated by a heating system, such as a plasma torch system, comprising two electrodes: a first electrode acting as cathode 13 (negative electrode) and a second electrode acting as anode 120 (positive electrode), as shown for example in
In the embodiment shown in
Some part of the charge (material being treated/heated) can be gasified, in which case it is collected with a filter dust system, which has a fume capturing means in the upper part of the furnace, around the upper ring. Fume is captured at the upper area of the furnace, conducted and extracted from the furnace through extraction conduit 25 (see
The furnace 1 also comprises a cover 21, as shown for example in
In operation, the furnace, in particular the crucible 12 and the material contained therein, is heated by a heating system comprising the two electrodes, cathode and anode, needed to allow current to flow from one electrode to the other one when a DC power supply with which the heating system is equipped, is switched on.
Cathode 13 is a movable electrode. In embodiments of the disclosure it is the movable part of a plasma torch. Due to its linear movement, it provides the furnace with the capability of power regulation according to the furnace operation conditions. The electrode acting as cathode 13 is inserted—thanks to its linear movement—through hole 26 into the tank 10, that is to say, into the volume 11 defined by the crucible 12. Thanks to the linear movement of the cathode plasma torch, the power at the input of the chamber can be adjusted, as the position of the movable electrode can be changed depending on the electric resistivity of the charge (melt, etc.). Through the hollow 26 made in the cover 21, electrode 13 projects in vertically displaceable manner into the volume defined by the crucible 12 and forms the cathode 13 for the DC arc. Cathode 13 therefore has linear movement capability.
Electrode 13 is held for example by a movable support arm 22 actioned with an electrically active connector 24, such as a clamp. Clamp has both mechanical and electrical functions (it holds the support arm 22 and makes the electrical wiring). Connectors 24 (such as clamps) also connect the electrodes—cathode 13 and anode (crucible) 12—with the required electric wiring 28. The electric wiring 28 is schematically represented in
In
Cathode 13 is made of an inorganic carbon-based material. Cathode 13 is preferably made of synthetic graphite having purity equal or above 98%. In other words, cathode 13 is preferably made of a material comprising at least 98% of synthetic graphite (percentage expressed by weight with respect to the total weight of the material) and an amount of ass content equal or less than 2% (percentage expressed by weight with respect to the total weight of the material). As a matter of example, the material of which the cathode is made may be produced using a raw material having at least 30% of needle coke.
As shown in
Inventors have observed that having an anode which corresponds to the crucible 12 provides the effect of having the same voltage potential difference all along the outer surface of the crucible. This makes the heating system more stable than conventional ones, in which the anode is implemented, for example, as a group of electric plates disposed in a certain portion of the crucible. As a consequence, the temperature of the material to be treated within the crucible is more stable. In other words, material (metal, waste, etc.) is treated in the anode itself.
At the start of the furnace operation, that is to say, at ambient temperature, the material to be loaded is preferably metallic, or at least having a similar electric conductivity as metallic materials, since for the startup a minimum electric conductivity is required, until a certain temperature is reached (for example, about 800° C.). This way, the loaded material also acts as anode in the plasma torch system. For example, an amount of metallic material filling the crucible with a depth of about 10 mm is required. The material is then melted under the heating action of the energy radiated by the plasma column 19 and keeps in liquid state in the crucible 12. Once the starting conditions are fulfilled and a certain temperature has been reached, the furnace can be loaded with non-metallic material (in general, with material with poor conductivity) to be melted, since at operation temperature non-metallic materials are conductive enough to substantially reach the same voltage as the anode. Non-conductive materials are melted due the effect of the plasma jet through radiation and convection heat transfer (until they reach temperatures higher than 1.000° C. for example). The electrons generated at the cathode 13 flow in the plasma column 19 and are collected at the surface of the molten bath 17 which acts as anode surface, thereby releasing their heat of recombination and heating the molten bath 17. The maximum level of molten metal is estimated to be, for example, about ⅔ of the chamber height (
In sum, the anode provides high conduction to current flow and stabilizes the plasma jet inside the cavity 11, because the crucible 12 provides a iso-electric potential surface. In this text, when it is said that the crucible is isopotential, an error or tolerance of about +/−1% is to be assumed. In particular, disturbances in the output voltage are lower than 5% of a setup objective. Setup objective is formed by selected voltage and intensity objectives in order to obtain desired power output. Voltage and intensity values are parameters of the heating process and relate to electrical conditions between anode and cathode.
When starting operation the charge (material) to be processed may be added in solid form (typically at ambient temperature) and then melted in the furnace. Alternatively, it may be directly transferred in liquid state from another furnace. Usually, the material to be treated is loaded in solid state, starting operation at ambient temperature and heating the furnace as explained, up to the adequate operation temperature, which depends of the process being carried out. The operation temperature is held for the time needed to process the material. The material—added for example in solid state—keeps in contact with the anode (because the whole crucible is anode, it is an iso-voltage area), as a consequence of which all material fed is substantially at the same voltage.
Charge (material being treated) is never solidified into the anode-crucible 12, as it has to be poured in liquid state out of the furnace. As already explained, liquid material is poured out of the furnace for example by tilting the furnace, or through manual extraction, or using pumping means, such as pneumatic pumping means, among others. For this reason (because the material to be treated must be extracted in liquid state, and therefore, the operation temperature must be kept high enough during the whole process), the crucible 12 and its surrounding layers (refractory layers and metallic frame) are not refrigerated, in order to prevent the material being treated from solidifying within the crucible 12. For this reason, optimized refractory layers need to be designed. Should the crucible be refrigerated, a much higher amount of energy would be required in order to keep the treated material in melted state until it is extracted from the furnace.
Turning back to the anode system,
In the embodiment of
The anode system 12, 12′, 12″ and the cathode 13 are easily replaceable. In particular, parts 12′ 12″ enable the easy replacement of the anode. Because anode system is made in this embodiment of three independent removable parts, and because the material around them (between anode graphite parts and refractory walls, such as concrete walls) is preferably self-sintering refractory, if needed, graphite parts can be disassembled and the self-sintered material is of easy removal. Thus, three main body of refractory concrete stays without damage and removed parts can be replaced easily.
As explained, the anode (crucible 12) is preferably made of a material comprising at least 98% of synthetic graphite (percentage expressed by weight with respect to the total weight of the material) and an amount of ass content equal or less than 2% (percentage expressed by weight with respect to the total weight of the material). In a particular example, the anode (crucible 12) is made of a material comprising at least 98% of synthetic graphite obtained from a material comprising more than 30% of needle coke and graphitized at a temperature of at least 2,800° C. The apparent density of the material is at least 1.6 g/cm3, preferably between 1.65 and 1.75 g/cm3. The selected synthetic graphite provides high conductivity properties both within the temperature melting range, typically of 600-1,600° C., and at room temperature, such as lower than 50° C. At both temperature ranges electrically short conditions (such as, for example, <10 Volt between anode and cathode) have to be obtained to allow current pass through the electric circuit. Therefore, the maximum resistivity allowed is 5.8Ω×μm measured in current pass longitudinal direction.
Thermal conductivity of the material of which the anode is made, is also a key property for easy homogenization of the thermal conditions inside de chamber 11 formed by the anode 12. The thermal conductivity of the material of which the anode is made must be larger than 125 W/Km, preferably larger than 200 W/km.
Because expansion and contraction process values of the different materials conforming the furnace are not the same, the anode 12 must be able to support expansion and contraction forces. Therefore, the material of which the anode is made must have bending strength of at least 9 MN/m2 and a Young's module of preferably between 8 and 10 MPa. Its linear strength must be at least of 4.5 MPa.
Layer 14A, which vertically surrounds the perimeter wall of the crucible 12, may be made of alumina-based corundum. In a particular embodiment, layer 14A is made of self-sintering alumina-based corundum having an amount of alumina (Aluminium oxide, Al2O3) larger than >85%, an amount of magnesia (Magnesium oxide, MgO) between 10 and 15%, an amount of Iron(III) oxide (Fe2O3) smaller than 0.3% and an amount of silica (Silicon dioxide, SiO2) smaller than 0.2% (percentages expressed by weight with respect to the total weight of the compound or composition). Grain size (largest dimension) is smaller than 6 mm and apparent density is between 2.6 and 2.9 gr/cm3. This material has a maximum working temperature of 1800° C. Layer 14A preferably extends downwards beyond the inner base of the crucible 12, but without extending beyond the whole thickness of the bottom portion of the crucible 12 (as average just as far as the middle thickness of the bottom part 12B of the crucible 12). Thickness of layer 14A may be between 5 to 30 mm.
A second portion or layer 14B of refractory material is disposed vertically surrounding the first layer 14A. This layer 14B may be made of alumina-based concrete. In a particular embodiment, layer 14B is made of alumina-based conformed concrete having an amount of alumina larger than 90% (preferably 94-97%) with contents of SiO2<0.5% and Fe2O3<0.5% (percentages expressed by weight with respect to the total weight of the compound or composition). Thickness of layer 14B os between 25-100 mm. Maximum working temperature of this material is above 1800° C., or above 1850° C.
A third portion or layer 14C of refractory material is disposed beneath the bottom portion of the crucible 12. It preferably extends radially, in such a way that it is also disposed beneath the first and second layers 14A 14B, as well as beneath the first elongated portion 12′ of the anode system. This layer 14B comprises calcined bauxite. It is capable of supporting a maximum temperature of 1,700° C. In a particular embodiment, layer 14C is made of a mixture of calcined bauxite in an amount between 80-90% and alumina-based concrete in an amount between 10-20% (percentages expressed by weight with respect to the total weight of the compound or composition). The thickness of the layer 14C may be variable. For example, its thickness may be larger beneath first and second layers 14A 14B than beneath the bottom part of the crucible 12. Average thickness of layer 14C at the bottom of the crucible is between 50-100 mm. A small layer 14C′ of the same material as layer 14C surrounds the upper end of part 12″
A fourth portion or layer 14D of refractory material is disposed vertically surrounding the second layer 14B. This layer 14D is the last refractory wall before the metallic frame 15. Layer 14D preferably extends downwards with respect to the third layer 14C, in such a way that is surrounds all previous refractory portions disposed around the crucible 12. This layer 14B also comprises calcined bauxite. It is capable of supporting a maximum temperature of 1,500° C. In a particular embodiment, layer 14D is made of a mixture of calcined bauxite in an amount between 77-85% and alumina-based concrete in an amount between 15-23% (percentages expressed by weight with respect to the total weight of the compound or composition). Average thickness of this layer is between 50-250 mm.
Surrounding the second elongated portion 12″ of the anode system which extends vertically from the first elongated portion 12′ thereof, there is a layer or portion 14E of refractory material. It may be a silica-based self-sintering refractory. Because the maximum temperature at this portion 12′ is lower than the temperature at refractory walls closer to the crucible, a material having lower sintering temperature may be used, such as a silica-based self-sintering refractory.
The space (if any) between the outer furnace frame and the detailed refractory layers may be filled with isolating fibre and low density isolating bauxite refractories. These materials may also be used for filling layer 14F at the bottom of the furnace. All these layers or portions 14A-14F provide high isolating capacity.
By controlling the furnace atmosphere, the content of free oxygen inside the chamber 11 is minimized, for example reduced to less than 1%. The furnace atmosphere is controlled (low oxygen content) using an inert gas purge inserted through the cathode and adding reducing material (carbon-base) with the material to be heated. In the chamber 11 of the furnace 1, reduction-oxidation process reactions can be controlled by applying accurate temperature control and guaranteeing inner atmosphere specific conditions. The furnace may be used in reduction of metal oxides contained in ores, by-products and industrial wastes.
Next, several experiments involving metallurgic reactions, carried out with a furnace implemented according to the shown figures, are disclosed.
In a first experiment, tin oxides from non-ferrous detinning processes are reduced in a furnace as shown in
xSnO+yC=xSn+CO2
SnO+C═Sn+CO
CuO+C═Cu+CO
SnO2+2CO=2Sn+2CO2
Zn (s)(+Q)═Zn (g)
While fume is being captured and delivered to extraction conduit 25, a reoxidation process takes place (from Zn to ZnO, in this example). Reoxidation occurs while material is being melted within the furnace. Fume is extracted from the furnace as already explained.
Zn (g)+O═ZnO (g)
As a result of the reducing or refining process, molten metal bath is obtained with the following compositions: Sn: 85-95%; Cu: 5-15%; Fe: <0.2%; Ni: <0.2%; Zn<0.5%. Additionally, slag and filter powder are obtained, such as by-products.
Slag average composition is CuO<5%, SnO 10-25%, Fe2O3 5-15%, Al2O3 5-25% MgO<5%, SiO2 5-20% CaO 3-8% and variable amounts of C (<5% and Na2O<25%. Rest of elements <3%.
Filter dust composition is SnO 50-75%, ZnO 10-25%, Na2O 5-20% and resto of residual elements <3%.
In the same furnace used in the first experiment, a second experiment is made. It is a reduction refining process for copper oxides coming from shorting and stripping of non-ferrous copper based scraps, with average composition of: Cu<40%; CuO 60-90%; Sn<1%; Ni<1%; Fe<2%; Zn<5%; others (including for example SiO2, Al2O3, MgO, . . . ) <10%. It has been treated in the furnace at an average temperature between 1,150° C. and 1,300° C., with a minimum process temperature of 1,050° C. and a maximum process temperature of 1,350° C. Atmosphere is reduced as λ<1 (where λ value is CO2max/CO2=1+(O2/(21−O2)). Slag-conditioning elements containing different amounts of SiO2, Al2O3, Na3(AlF6), MgO and Fe2O3 are added and mixed with the tin oxide raw material. The following reactions are carried out in the chamber 11 defined by the crucible 12:
CuO+C═Cu+CO
xSnO+yC=xSn+CO2
SnO+C ═Sn+CO
SnO2+2CO=2Sn+2CO2
Zn (s)(+Q)═Zn (g)
And afterwards, in the fume capturing system:
Zn (g)+O═ZnO (g)
As a result of the reducing or refining process, a molten metal bath is obtained with the following compositions: Cu: >98%; Sn+Fe+Ni: <2%; Zn<0.5%.
In this text, the term “comprises” and its derivations (such as “comprising”, etc.) should not be understood in an excluding sense, that is, these terms should not be interpreted as excluding the possibility that what is described and defined may include further elements, steps, etc.
In the context of the present disclosure, the term “approximately” and terms of its family (such as “approximate”, etc.) should be understood as indicating values very near to those which accompany the aforementioned term. That is to say, a deviation within reasonable limits from an exact value should be accepted, because a skilled person in the art will understand that such a deviation from the values indicated is inevitable due to measurement inaccuracies, etc. The same applies to the terms “about” and “around” and “substantially”.
On the other hand, the disclosure is obviously not limited to the specific embodiment(s) described herein, but also encompasses any variations that may be considered by any person skilled in the art (for example, as regards the choice of materials, dimensions, components, configuration, etc.), within the general scope of the disclosure as defined in the claims.
Number | Date | Country | Kind |
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20382275.4 | Apr 2020 | EP | regional |
Filing Document | Filing Date | Country | Kind |
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PCT/EP2021/058161 | 3/29/2021 | WO |