• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a new type of central column for self-cooking compound electrodes in submerged arc electric furnaces, where a heart or metal column is used as a central support element compared to conventional graphite cores, and which is preferably manufactured with a hypereutectic alloy of aluminum-silicon, or iron, where said heart has a general star shape, being able to be a monobloc body with the hollow center or be formed by a central hollow tube independent of the plurality of projecting fins of radially joined together, and wherein said central gap is filled with a silicon carbide precursor. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2724498A1
    申请号:ES201830212
    申请日:2018-03-05
    公开日:2019-09-11
    发明作者:Camarasa Francisco Javier Bullon
    申请人:Silbucam S L；
    IPC主号:
    专利说明:

    [0001]
    [0002]
    [0003]
    [0004] Central column for self-cooking electrodes in electric submerged arc furnaces.
    [0005]
    [0006] FIELD OF THE INVENTION
    [0007]
    [0008] The central column object of the present invention replaces the conventional graphite core or core of the self-cooking composite electrodes that are used for the production in submerged arc furnace of silicon metal and other ferroalloys, defining in this invention a Concentric hollow metal column with the outer ferrule of the electrode and in which the same double sliding system of the composite electrode can be applied. This central column has a special way to favor the mechanical support and the cooking of the carbonaceous paste either in the form of a tube with fins or in the form of a star, and that is made of metallic materials, but not contaminants for silicon due to similarity of composition and preferably with a hypereutectic aluminum-silicon alloy. For ferroalloys where iron is not a contaminant this metal column could also be made of iron. Inside the tube or star a silicon carbide precursor is placed to fill the gap generated by the melting of the metal structure at the bottom of the electrode.
    [0009]
    [0010] The field of application of the present invention is the industrial sector of silicon metal and the ferroalloys produced in an electric submerged arc furnace.
    [0011]
    [0012] STATE OF THE PREVIOUS TECHNIQUE
    [0013]
    [0014] Within the technical field related to submerged electric arc furnaces, it is known that one of the fundamental elements are electrodes. As a general rule, the electrodes consist of a carbonaceous mass that transmits the electric current to the bottom of the furnace where the electric arc jumps between the electrode and the hearth of the furnace, which produces the energy necessary to reduce minerals, generally of oxides, and obtain the product, for example: Quartz, which is silicon dioxide (SiO2), by reaction with coal and consuming a large amount of energy, silicon is obtained. This arc wears the electrode that is replaced by the top of the column and descends as it is consumed. There are several types of electrodes from the so-called precooked ones, whose state and shape does not vary in the column because they have already been cooked in the producer's factory such as graphite, and those that, instead, are cooked with the heat itself from the oven as the column that is usually called self-cooking descends, highlighting in turn two types: the so-called Soderberg pasta electrodes whose sole elements are the ferrule and the carbonaceous paste that is cooked inside the ferrule and the so-called as compounds because part of it is precooked and part is cooked as it descends with the heat of the oven itself.
    [0015]
    [0016] The Soderberg type electrodes are composed of a metal ferrule that is used as an envelope of the Soderberg paste which is a mixture of various particle sizes of various types of coal along with a pitch that acts as a binder. The pitch is liquefied between 60 and 100 ° C, so that the paste that is transported and used as a solid material, when entering the top of the electrode column at room temperature, becomes a liquid that fills the ferrule totally when going from 100 ° C to about four meters above the oven. Upon reaching the temperature around 400 ° C, the paste hardens again, being cooked with the round shape of the ferrule and maintaining this structure when the ferrule melts and is introduced into the oven mixture until it is consumed in the electric arc of The bottom of the electrode. The weight of the whole mass of coal that constitutes the pasta is supported by the ferrule that has on its inner surface a series of conveniently perforated metal fins where the pasta sticks when cooked and that supposes the mechanical support of all cooked and uncooked pasta . These fins are welded to the ferrule, descend together with it and also melt at the bottom of the electrode, but when the paste is already well cooked.
    [0017]
    [0018] This is the system used for many years in all ferroalloys where the iron supply produced by the ferrule is admissible for the quality of many products such as the whole family of ferrosilicon, ferroamanganese, silicomangannese or ferrochromes.
    [0019] In silicon metal, the iron contamination of the ferrule is not admissible since the iron percentage must be below 0.5%, so pre-cooked electrodes that are of lower quality and price than those of graphite and of much larger diameter These electrodes are cylindrical blocks of about two meters in height and variable diameter according to the power of the oven that are normally between 1 m and 1.40 m. There are few factories in the world of this type of electrode and they are an expensive and important product within the cost price of silicon.
    [0020]
    [0021] On the other hand, the principle of the operation and introduction of the electrodes in the oven as consumed by the arc at the bottom is by means of sliding rings that are generally two: the fixed and the mobile and have their own structure at about 8 meters above the oven and that is part of the structure of the electrode column. The weight of the entire column of electrode that is consumed, is normally supported by the two rings, but when you want to slide from the rest position the movements are: the fixed ring is opened, the closed mobile ring that drags is slid or lowered to the electrode and introduces it in the oven in the programmed length, the fixed ring that will support the entire electrode is closed, while opening and raising the mobile ring to the rest position, where it closes leaving the two rings in the original situation. So on, the sliding rings are always in the same place of the column, what drags the mobile ring is the metal ferrule inside which is the carbonaceous paste with the corresponding phase change from solid to liquid and again solid according to the height
    [0022]
    [0023] The ferrule can have on its surface a series of metal fins where the pasta is glued when cooked and that supposes the mechanical support of the whole weight of the pasta that is above the cooking zone. These fins are welded to the ferrule, descend together with it and also melt at the bottom of the electrode.
    [0024]
    [0025] On the other hand, the technology is known where a composite electrode is developed that has a heart or central column of graphite and the rest is the same Soderberg-type carbonaceous mass and ferrule mentioned above. This solution includes two totally differentiated sliding systems, one for the graphite core and the other for the ferrule. In this way, when sliding the graphite with the ring of the ferrule closed, only the carbon glided because the ferrule remained motionless and like the paste Soderberg was already sufficiently cooked and solid in the area where the ferrule disappeared, the contamination was zero or negligible. This solution is based on patents US4575856 by John Persson and patent US5351266 by Bullón et al. In this composite electrode the mechanical support of the column is entrusted to the adhesion between the central graphite electrode and the paste when cooked. The cooked pasta area is higher in the graphite environment than in its outer surface that is in contact with the ferrule. In addition, graphite is a more porous material than iron ferrule and that is why graphite paste adhesion is much superior to ferrule paste and when sliding graphite lowers the entire carbon electrode breaking the ferrule paste junction and leaving the ferrule sliding which does not contaminate silicon. The ferrule in this type of composite electrode is completely smooth inside, it has no fins, so that the paste paste connection is always inferior to the paste graphite. This technology was a total success, and today, more than two decades later, it is implanted in multiple furnaces worldwide.
    [0026]
    [0027] The present invention supposes a new generation of compound electrode in which the heart or graphite column is replaced by another type of central column. It should be borne in mind that the technologies known to date, including the one described above, present the problem and technical inconvenience that graphite is a fragile material with low tensile and flexural strength. In addition, it is a material that can have manufacturing deficiencies that are almost impossible to detect by the customer and that lead to unexpected breaks in the electrode column that are very expensive and difficult to solve in factories. In fact, technical characteristics are cited in all catalogs of graphite manufacturers, but always with the clarification that they are average figures that are not guaranteed.
    [0028]
    [0029] Taking into account this technical problem, the present invention solves the objective technical problem of guaranteeing a central column with a better tensile and flexural strength, including its possibility of plastic deformation, and that improves the performance of the graphite cores. For this reason, the present invention describes a solution in which the graphite core is replaced by a central metal column with characteristics that are detailed below, and not of coal or any of its variables such as carbon fibers or another type of electrode that was not graphite.
    [0030] EXPLANATION OF THE INVENTION
    [0031]
    [0032] The present invention describes a new type of electrode composed of self-cooking where the heart of graphite is replaced by a central metal column, a central column that is also referred to as the heart in the sector. The advantage of a metal central column, compared to one of graphite, is its better tensile and flexural strength, including its possibility of plastic deformation.
    [0033]
    [0034] In this regard, it should be noted that a central iron column has much better mechanical characteristics than any graphite, but it has a disadvantage that makes it unusable in the manufacture of silicon, which is the contamination above the maximum 0.5% Fe that they admit Silicon customers.
    [0035]
    [0036] Therefore, the object of the present invention is the use of a metallic material for a central electrode column that does not contaminate and that has much better mechanical characteristics than graphite. This is solved by the preferential use of aluminum and silicon hypereutectic alloys. Silicon itself does not pollute and it is also known that aluminum is one of the easiest pollutants in liquid silicon by oxidation in the spoon itself where liquid silicon is collected at the exit of the oven. For the entire aluminum market that accounts for over 40% of the demand for silicon, it is clear that the percentage of aluminum is not important and the removal of aluminum is very simple.
    [0037]
    [0038] Pure aluminum, or even the eutectic that contains 12% silicon, could be used, but it has the disadvantage of its low melting point and that it loses its mechanical characteristics very quickly as the temperature increases. Therefore its use is not recommended since it would lose them even before it would be at the point of solidification and that is the reason why producers who use compound electrodes exclusively use the core / central column of graphite of the patents defined in the previous section. On the other hand, as can be seen in the diagram (Fig. 2) of Al-Si phases, as the percentage of silicon increases, the melting temperature increases significantly to reach 100% silicon, which would be 1402 ° C.
    [0039]
    [0040] Trials have been conducted where it is observed that Al-Si hypereutectic drugs improve mechanical characteristics of graphite, compared to these values in Table 1:
    [0041]
    [0042]
    [0043]
    [0044]
    [0045] Table 1
    [0046]
    [0047] Al-Si hypereutectic alloy data are verified by laboratory tests at Research Institutes, scientific publications and manufacturers catalogs. Graphite data is obtained from manufacturers' catalogs for HP middle class electrodes; high UHP and the nipples ( connected electrodes) that have a special treatment. In the data (Table 1) of the Al-Si hypereutectic alloy it can be seen that the solidification form of the product is fundamental. The GC product has had a direct solidification with which it has first solidified the silicon and then the aluminum, this has created silicon crystals that greatly damage the mechanical characteristics, even so, in the worst case it is 4 times higher Graphite But, the form of extra fast solidification by spraying the metal by means of gas countercurrent, for example, nitrogen and others, and subsequent pressing of the powder at temperatures below 500 ° C, greatly improves these characteristics. In addition, the characteristics can be improved by adding in the liquid phase certain elements such as Cu and / or graphite and / or others according to known techniques for improving characteristics within the aluminum sector.
    [0048]
    [0049] Therefore, the self-cooking electrode of the present invention is composed of an outer ferrule with a smooth wall inside and with a concentric inner column of a metallic and non-carbonaceous nature, which is not known to date in this industrial sector. The ferrule and the central column have different sliding rings similar to the composite electrode described above. The central column of the The electrode is made of a hypereutectic Al-Si alloy in which the percentage of silicon is between 25 and 80%.
    [0050]
    [0051] Entering the configuration of the electrode of the invention, the physical form of said heart or central column and how they are connected between them is essential, as well as developing a solution that favors the adhesion between the paste and said central column. In all cases the central column is an element of length between 2 and 3 meters and variable diameter, depending on the diameter of the oven electrode, in the same way that the diameter of the graphite in the composite electrode is now variable.
    [0052]
    [0053] There is a first possible configuration, which consists of a round massif, similar to the heart of graphite, which would have the advantage of its lower manufacturing cost and the disadvantage that the surface of adhesion between paste and metal is only the surface of the circumference. Said surface could be rough to favor adhesion. However, this configuration presents the problem that, at the time of melting, it generates holes that can produce fragility zones in the electrode assembly.
    [0054]
    [0055] For this reason, the present invention discloses a solution that is based on a central column with a plurality of radial fins that depart from a hollow tube, thereby allowing the column to have a star shape. The tube has an outer central diameter between 90 and 350 mm and an inner diameter between 40 and 250 mm sufficient to give the mechanical resistance to the assembly, which preferably leaves between 4 and 10 fins or slightly conical arms and with a rounded tip of much more thickness reduced between 5 and 30 mm and lengths between 40 and 380 mm designed to significantly increase the contact surface between the metal and the paste. These fins may in turn be perforated so that the paste when introduced into said perforations works at a cut, increasing the mechanical strength of the assembly. In the solution of the present invention, in order to solve the fragility problems described above in the first case of the solid cylinder, the central column is in the form of a hollow tube, so that in the center it is possible to introduce a third material that when reacting With the aluminum-silicon hypereutectic, shortly before melting, it will delay this fusion and maintain the mechanical support of this central column for a longer time. This filler material consists of a silicon carbide precursor that is formed by reaction of silicon with coal at high temperatures. This precursor may consist of:
    [0056] - Insert silicon powder in granulometry smaller than 2 mm into the tube and graphite powder in the same particle size and with stoichiometry of the C + Si reaction, finally obtaining CSi. In this solution, the entire column is kept filled to the top of the electrode, to favor the absence of oxygen and the gradual increase in temperature. When the heart or metal column is melted, the carbon powder reacts with the silicon of the tube forming carbides that are slightly expansive in volume and fill the space previously occupied by the tube and the fins, improving the mechanical resistance of the electrode; or
    [0057] - fill the inside of the tube with a rolled graphite blanket. This is a flexible and very porous material, which absorbs the silico-aluminous metal by capillarity, so that it expands very flexibly, fills the entire gap and leaves a silicon carbide alloy inside the graphite blanket that also favors The mechanical resistance of the electrode. This blanket is a material composed of a matrix of interwoven graphite threads, so that the blanket is porous, and when the metal dissolves, this liquid is absorbed by the blanket, it inflates and fills the gaps avoiding weak or fragile areas of the column at the bottom of the oven.
    [0058]
    [0059] In another embodiment of the present invention, the column can be configured by two differentiated elements, the metal central tube and the metal fins as separate elements which can also greatly improve the mechanical resistance and reduce the manufacturing of the central column of the composite front electrode. to the current graphite. In this case, the central tube has between 3 and 10 notches on its outer surface where a projection enters that fits perfectly in the notch that is made to the fin at one of its two ends. The other end of the fin has a rounded termination. These are two different pieces, both manufactured for use in the manufacture of silicon metal with majority silicon alloy in the form of Al-Si hypereutectic.
    [0060]
    [0061] These same ideas can be applied to the rest of the ferroalloys, in which the use of iron has no contamination problems, which normally use metal ferrule with inner fins and is consumed when the electrode slides. The reason is that it is much easier to connect the central metal electrode body than to weld a ferrule that is consumed almost every day and requires between 2 and 3 hours of two good welders. The central column prevents systematic sliding of the ferrule by the principle of the double sliding system of the composite electrode and is cheaper than the sum of the cost of the ferrule and its assembly time in the column. Therefore, in another preferred embodiment of the invention, the metal column may be iron.
    [0062]
    [0063] The form of connection between these central bodies of the electrode is by means of plates, which are fastened to the two bodies by means of screws or round passages from one side to the other of the central column. The mechanical resistance to traction by the weight of the electrode marks the dimension of the plates and the through holes that can be two or more in the space between the fins, as can be seen in the attached drawings. In the case of using the star-shaped monobloc configuration, the plates can be screwed to the arms of the star so that the two upper and lower elements are joined very easily and quickly, as can be seen in the subsequent figures. The way of descending the electrode inside the oven is by means of sliding rings which in general are two: one fixed and one mobile. The electrode is normally supported by the two, but when you want to slide from the rest position the movements are: the fixed ring is opened, the closed mobile ring that drags the electrode is slid or lowered, the fixed ring is closed, the fixed ring is opened, and raise the moving ring to the rest position. So on, the sliding rings are always in the same place of the column, what drags the mobile ring is the metal ferrule inside which is the carbonaceous paste with the corresponding phase change from solid to liquid and again solid according to the height.
    [0064]
    [0065] It should be borne in mind that, throughout the description and the claims, the term "comprises" and its variants are not intended to exclude other technical characteristics or additional elements. In addition, in order to complete the description and to help better understanding of the features of the invention, a set of figures and drawings is presented in which the following is represented by way of illustration and not limitation:
    [0066]
    [0067] Figure 1. Diagram of the assembly of a self-cooking electrode with a central column in a submerged electric arc furnace.
    [0068]
    [0069] Figure 2. Representation of the Al-Si phase diagram where it is observed that as the percentage of silicon increases, the melting temperature increases so important to reach 100% silicon at a temperature of 1402 ° C.
    [0070]
    [0071] Figure 3. Perspective view of the internal structure of a way of bringing the electrode of the present invention into practice.
    [0072]
    [0073] Figure 4. Plan view of the previous figure.
    [0074]
    [0075] Figure 5. Schematic representation of a star-shaped electrode column where the core and fins is a monobloc element.
    [0076]
    [0077] Figure 6. Plan view of the previous figure.
    [0078]
    [0079] DESCRIPTION OF THE DRAWINGS
    [0080]
    [0081] As can be seen schematically in Figure 1, the present invention describes a self-cooking compound electrode (E), with a differentiated core (1) and serving as a mechanical support, which has at least one set of slip rings (2) for said core (1), and a second set of rings (3) for a metal outer ferrule (7) without inner fins, which is filled by a carbonaceous paste, and which is represented in its three phases : Initial solid (4), liquid below (5) and cooked (6). The cooking of the pasta is carried out by the heat that is communicated from the oven itself and is transmitted by the coal itself and the central core and mainly through the electrical energy that is introduced through the contact plates (9) of the electrode. With this, the pasta obtains the stiffness and consistency under plates in the cooked zone (6) to continue descending, only the pasta cooked in the column until it reaches the submerged arch or lower zone (8) of the oven where temperatures are reached in the environment of 2500 ° C. This figure serves both for the present invention where the column is metallic and for conventional graphite heart electrodes.
    [0082]
    [0083] In a first embodiment of the invention, as seen in Figures 3 and 4, the core (1) of the electrode is a central column consisting of a hollow tube and a plurality of radial fins, which confer the body in its block of a star shape, all formed by a metallic material, such as an aluminum-silicon hypereutectic material. Specifically, the hollow of the core / center of the tube (10), starting and protruding from the tube (10) radially the fins (11) of much smaller thickness intended to significantly increase the contact surface between the metal and the paste (14), leaving the core (1) and the concentric paste (14) protected externally by the ferrule (7) which is the diameter of the electrode that will be introduced into the oven below. These fins can in turn be perforated or have perforations (110) so that the paste when introduced into said perforations works at an increased cut the mechanical resistance of the assembly. The central column is in the form of a hollow tube or cylinder (10), so that a filling material (15) can be introduced into the central hollow, which, when reacting with the aluminum-silicon hypereutectic when melted, delays that fusion and maintains it during longer the mechanical support of this central core (1). This filler material (15) consists of a precursor, preferably silicon carbide. In this first embodiment, the hollow cylinder or tube (10) has a plurality of notches (101) where the initial end of each of the fins (11) produced from the same alloy is introduced, but independently. The different cores (1), between 2 and 3 meters high, are joined by pins (13) or through the ends of the column in turn joined by plates (12) without the need for any welding, so it is allowed to create an electrode of the necessary height.
    [0084]
    [0085] In a second embodiment of the invention, as seen in Figures 5 and 6, the electrode core (1) is a star-shaped column of metallic material, for example an alloy of Al-Si hypereutectic material, all in a single monobloc body where there is a central part in the form of a hollow cylinder (10) with a central diameter, from which a plurality of fins (11) leave radially to significantly increase the contact surface between the metal and the paste ( 14), leaving the core (1) and the paste (14) concentric externally by the ferrule (7) which is the diameter of the electrode that will be introduced in the oven below, and where stability is ensured by means of pins (13 ).
    权利要求:
    Claims (12)
    [1]
    1. - Central column for self-cooking electrodes in submerged arc electric furnaces, where the electrode is of the composite type and comprises a core, a carbonaceous paste that covers it and an outer concentric ferrule that covers the core and the paste and which is the diameter of the electrode that is introduced into the oven; arranging both the ferrule and the core of different sliding rings for its introduction and descent into the oven; where the central column is characterized in that the core (1) is constituted by a central tube (10) that is hollow and of metallic material, and a plurality of fins (11) of metallic material that protrude and leave radially from the tube (10 ); and where a filler material (15) consisting of a silicon carbide precursor is introduced into the tube recess (10).
    [2]
    2. - Central column for self-cooking electrodes in electric submerged arc furnaces, according to claim 1, characterized in that the metallic material is an Al-Si hypereutectic alloy.
    [3]
    3. - Central column for self-cooking electrodes in electric submerged arc furnaces, according to claim 2, characterized in that in the Al-Si hypereutectic alloy the percentage of silicon is between 25 and 80% .
    [4]
    4. - Central column for self-cooking electrodes in electric submerged arc furnaces, according to claim 1, characterized in that the metallic material is iron.
    [5]
    5. - Central column for self-cooking electrodes in electric submerged arc furnaces, according to claim 1, characterized in that the precursor is a mixture of silicon powder in granulometry smaller than 2 mm and graphite powder in the Same grain size.
    [6]
    6. - Central column for self-cooking electrodes in electric submerged arc furnaces, according to claim 1, characterized in that the precursor is a rolled graphite blanket consisting of a weave of interwoven graphite wires.
    [7]
    7. - Central column for self-cooking electrodes in electric submerged arc furnaces, according to claim 1, characterized in that the number of fins (11) that split and project radially from the tube (10) is between 4 and 10.
    [8]
    8. - Central column for self-cooking electrodes in electric submerged arc furnaces, according to claim 1, characterized in that the fins (11) have perforations (110).
    [9]
    9. - Central column for self-cooking electrodes in electric submerged arc furnaces, according to claim 1, characterized in that the different cores (1) are joined by pins (13) at the ends of the heart attached to their once by plates (12) not welded.
    [10]
    10. - Central column for self-cooking electrodes in electric submerged arc furnaces, according to any of the preceding claims, characterized in that the hollow central tube (10) and the plurality of wings (11) are independent, and they are connected by introducing the initial end of each of the fins (11) into notches (101) enabled for this purpose on the surface of the hollow tube (10).
    [11]
    11. - Central column for self-cooking electrodes in submerged arc electric furnaces, according to claim 10, characterized in that the tube (10) has an outer central diameter between 90 and 350 mm and an inner diameter between 40 and 250 mm; and the fins (11) are conical and rounded, where the thickness is between 5 and 30 mm and has lengths between 40 and 380 mm.
    [12]
    12. - Central column for self-cooking electrodes in electric submerged arc furnaces, according to any of claims 1 to 9, characterized in that the tube (10) and the plurality of fins (11) form a monobloc body .
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    同族专利:
    公开号 | 公开日
    WO2019170941A1|2019-09-12|
    ES2724498B2|2020-01-17|
    EP3764742A1|2021-01-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3524004A|1968-12-03|1970-08-11|Ohio Ferro Alloys Corp|Non-metal reinforced self-baking electrode for electric furnaces|
    US4756813A|1986-10-24|1988-07-12|Stanley Earl K|Self-baking electrode|
    DE1440564B2|1959-04-11|1972-02-17|Societe Edison-Settore Chimico S.p.A.-Azienda Industriale San Marco, Mailand |ELECTRIC ARC OR REDUCING FURNACE|
    DE4010353C2|1990-03-28|1993-04-22|Mannesmann Ag, 4000 Duesseldorf, De|
    CN201904937U|2010-12-24|2011-07-20|登封电厂集团铝合金有限公司|Combined electrode self-baking device capable of unshelling for large submerged arc furnace|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201830212A|ES2724498B2|2018-03-05|2018-03-05|CENTRAL COLUMN FOR SELF-COOKING ELECTRODES IN SUBMERGED ARC OVEN OVENS|ES201830212A| ES2724498B2|2018-03-05|2018-03-05|CENTRAL COLUMN FOR SELF-COOKING ELECTRODES IN SUBMERGED ARC OVEN OVENS|
    PCT/ES2019/070111| WO2019170941A1|2018-03-05|2019-02-27|Self-baking electrode for submerged electric arc furnaces comprising a center column|
    EP19717961.7A| EP3764742A1|2018-03-05|2019-02-27|Self-baking electrode for submerged electric arc furnaces comprising a center column|
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