ES2915668T3 - Procedure for the manufacture of a coking product - Google Patents

Abstract

Process for manufacturing a coking product (VK) formed by solidifying a carbon-bearing material that is intended for use in the production of metals, metal alloys and metallurgical products or as an intermediate product for the manufacture of graphite elements and that has a monolithic geometry close to the final dimension and a density of at least 1.4 g/cm3, comprising the following work steps: a) provision of a container (2,202), which - encloses an interior space (3) and - comprises a filling opening for filling the interior space (3) with a fluid carbon-bearing material (K), as well as - heating equipment (10,210) for heating the carbon-bearing material (K) filled in the interior space (3) of the container (2,202); b) introduction of the fluid or pourable carbon-bearing material (K) through the filling opening into the interior space (3) of the container (2,202), the carbon-bearing material (K) comprising at least one coking carbon component fluid or meltable, as well as, optionally, at least one solid coking carbon component and, also optionally, at least one additive serving to adjust the properties of the carbon-bearing material (K); c) heating the carbon-bearing material (K) filled in the interior space (3) of the container (2,202) by means of the heating equipment (10,210) at a coking temperature, keeping the carbon-bearing material (K) heated at the corresponding coking temperature in each case at the coking temperature until the carbon-bearing material (K) held at the coking temperature solidifies by coking into the coking product (VK), - taking place, during the working stage c), a relative movement oriented along the longitudinal axis of the container (2,202) between the carbon carrier material (K) heated in each case and the heating equipment (10,210), - covering the heat emitted by the heating equipment (10,210 ) in each case only a partial volume - which extends over a certain partial section of the height of the interior space (3) of the container (2,202) - of the carbon-bearing material (K) filled in the e inner space (3), and - or the carbon-bearing material (K) filled in the inner space (3) of the container (2, 202) remains stationary while the heating zone (10, 210) moves starting from the base arranged downwards in the direction of gravity opposite to the direction of gravity in the direction of the upper end of the container (2,202), or - the heating equipment is arranged stationary and the carbon-bearing material (K) filled in the container (2,202 ) is moved relative to the heating equipment (10,210) either the container with the carbon carrier material filled inside moving along the stationary heating equipment or a discharge opening being provided at the base of the container (202) by means of from which the coking product (VK) is continuously withdrawn from the vessel (2,202) as a filament formed by the carbon carrier material (K) solidified in each case (working steps)); and d) discharging from the container (2,202) the gas that escapes from the carbon-bearing material (K) during heating and holding (step c)); e) extraction of the coking product (VK) out of the vessel (2,202).

Description

DESCRIPTION

Process for the manufacture of a coking product

The invention relates to a process for the manufacture of a coking product formed by solidification of a carbon-bearing material that is intended for use in the production of metals, metal alloys and metallurgical products or as an intermediate product for the manufacture of elements of graphite and having a geometry close to the final dimension and monolithic and a density of at least 1,4 g/cm3

Coking products of the type manufactured and of the nature according to the invention are used, for example, as anodes in the production of aluminum or as electrodes in the smelting or metallurgical treatment of steels in electric arc furnaces and in reduction furnaces. .

An overview of the current state of the art in the field of electrode fabrication for the metallurgical treatment of metals or metal alloys can be found in the article by Rick Adams, Wilhelm Frohs, Hubert Jager and Keith Roussel "Graphite Electrode and Needle Coke Development ", published by the American Carbon Society in 2007, which is available for download at http://acs.omnibooksonline.com/data/ papers/2007_D031(K).pdf.

Consequently, for the manufacture of coking products of the type with which we are concerned here, the coal is provided in solid form, generally as coke. The coke is generally produced in a manner known per se from residues resulting from crude oil refining or other petrochemical processes. In this connection, carbon carriers that can be coked, such as residues produced during petroleum distillation or similar carbon carriers, are subjected to a coking process. Alternatively, coal tar pitch is used as a coking feedstock. If necessary, the so-called green coke is subjected to a calcination process to remove the volatile hydrocarbons still present in particular in petroleum coke.

So-called needle coke is typically used for applications where a high mechanical load carrying capacity is required with minimal simultaneous thermal expansion, for example in smelting or metallurgical treatment of steel in an electric arc furnace. This represents the highest level of quality and can only be manufactured with greater effort (DE 102004 035 934 A1). For applications where lower requirements are placed on mechanical load-carrying capacity or thermal expansion behavior, the expensive needle coke can be partially or fully replaced by a less expensive type of coke or by one of the other carriers. carbon (for example, anthracite coal).

The coke is ground until it reaches a grain size suitable for consumption, from which eight grain fractions are usually separated by screening. Normally, coke of different grain fractions is mixed to form a mixture of coke grains with a grain size distribution that is considered optimal with respect to the properties of the graphite element that it is desired to adjust. Normally, mixtures consisting of one-third powder and two-thirds grain are produced in this connection, in order to ensure sufficient density. In this sense, it is assumed that the coke powder fills the gaps between the coke grains. Additives such as, for example, iron oxide can be added to the respective mixture. The iron oxide minimizes the irreversible thermal expansion of the coke ("puffing") that occurs during subsequent heat treatments when the sulfur still present in the coke is expelled from the carbon lattice.

The grain mixture, normally preheated to reduce processing times, is mixed with a binder such as coal tar pitch, stearic acid, or mixtures of these binders, to form a plastically deformable, homogeneous, pasty mass whose binder proportion is usually be from 20 to 24% by weight. The carbon-binder mass obtained, which is also called "green mass" in technical jargon, is converted into the so-called "green compact" by pressing, extrusion, vibration or tamping: During this molding operation, the temperature is below the mixing temperature, so at this point there is a very viscous mass.

The green compacts are then slowly heated to between 800 and 950°C in the absence of oxygen. During this combustion process, part of the binder breaks down into gas, which must escape from the green compact. This development of gases causes heating that progresses slowly because, otherwise, the pressure of the gas that is generated in the green compact could cause the formation of cracks and, concomitantly, the instability of the carbon or graphite element that leaves. to manufacture.

Depending on the binder system used, approximately one third of the mass of the binder used is lost during the firing process. The degassing of the green compact binder leaves cavities in the intermediate product obtained after firing through which the intermediate product has a reduced density. This, as a general rule, is not sufficient for the manufacture of carbon or graphite elements for which high electrical conductivity and high resistance are required, such as, for example, graphite electrodes for melting or treating steel. Therefore, the intermediate product obtained after the first firing is usually subjected to the so-called "impregnation" before further processing. To do this, it is introduced under pressure into the product intermediate a heated impregnating agent that has a lower viscosity than the binder originally used, usually coal tar pitch, to fill the pores in it. The intermediate product is then recooked. In this connection, part of the previously injected impregnating agent evaporates, with the result that the intermediate product inevitably has open pores which are not filled with carbon, even after an impregnation step. Consequently, the impregnation operation must be repeated if necessary until the intermediate product has the necessary density for further processing.

For further processing to become a top quality graphite element, the intermediate product undergoes a graphitization process. In this regard, by heating it up to about 2800 °C, the carbon contained in the intermediate product turns into graphite, which is characterized by an increasingly three-dimensional arrangement of the carbon atoms. Normally, the so-called "Acheson process" or the cheaper "Castner process", the so-called longitudinal graphitization (LWG), are used in this case. The lowest possible sulfur and nitrogen content of the starting material and the consequent low tendency to swell favor the process and the success of the graphitization. The negative effect of nitrogen and sulfur still contained in the intermediate product, as mentioned, can also be reduced by suitable additives, such as iron oxide, or selective temperature control during graphitization.

Methods based on the so-called "Soderberg process" (see, for example, US 1,440,724 A, US 1,640,735 A) avoid the effort involved in manufacturing graphite electrodes by forming a green compact, firing the compact green to become an intermediate product and the graphitization process.

In one design of this process described in US 3,365,533 A, a pasty carbon carrier material consisting of a mixture of granular coke and liquid tar distillate serving as a binder is packed into a tubular housing of an electrode which is introduced with a end in the furnace chamber of a reduction furnace (arc furnace) for the melting/reduction of, for example, phosphorus, tantalum or ferromanganese from ores. The electrode housing is made of an electrically conductive carbon steel. A current is applied to the electrode housing which is transmitted to the carbon carrier material filled in the housing. In this way, an electric arc is ignited in the furnace chamber whereby the temperatures in the area of the end of the electrode that enters the furnace chamber rise to more than 2000 °C. As a result, a temperature gradient is created in the carbon-bearing material contained in the electrode housing whereby the pasty carbon-bearing material in the upper part of the electrode is kept molten at about 200 °C. In the direction of the end of the electrode associated with the furnace chamber, the temperature of the carbon support increases continuously. In this connection, the hydrocarbon compounds contained in the carbon material decompose in the temperature range from 400 °C to 600 °C. The gases released in this way must be able to escape towards the upper end of the electrode which enters the furnace chamber. At the same time, the carbon from the hydrocarbon compounds must fill the free spaces between the coke grains. With increasing approach to the tip of the electrode entering the furnace chamber, this process continues until the carbon-bearing material appears the tip of the electrode, which enters the furnace chamber as a solid and compact body. In melting operation, the electrode is consumed and must be pushed from above to maintain the electric arc in the furnace chamber.

In another variant of the Soderberg method described in DE 60001 106 T2, an electrode with a cylindrical container is also arranged in a furnace for melting a steel alloy, which is guided with its open upper end through the furnace wall. The container is made of conductive stainless steel. Through its open upper end, the container is fed with an unbaked electrode mass. On its way to the lower end of the container, which is also open, the electrode mass is liquefied by the heat supplied through hot air guided in a central zone around the electrode container until it reaches the zone of an arrangement in form of a plate located next to the lower outlet opening of the container to couple an electrical current. As a consequence of the high temperatures that prevail in the area of the tip of the electrode that enters the furnace chamber, the mass of the electrode is also fired "in situ" there. The solid electrode filament of the electrode mass thus baked is continuously conveyed from the lower outlet opening of the container into the furnace chamber and serves as an electrode for supplying the electrical energy by means of which the arc is kept going. electrical and, therefore, the melting process in the furnace. Nor is the problem of guaranteeing a certain density of the graphite element produced in this way addressed in this sense, such as the adjustment of certain mechanical or other properties that are relevant for the use of the coking products referred to in the invention.

In addition to the state of the art described above, document US 4,472,245 A discloses a process for the thermal treatment of carbonizable materials, such as wood, paper, plastic, rubber, mineral substances containing hydrocarbons, petroleum shale and oil sand, with the aim of producing gas from raw materials. For this, the material to be charred is introduced in bulk into the furnace chamber of an electric shaft furnace through a filling opening. A first vertically aligned electrode enters the furnace chamber and is supported by the furnace lid, reaching with its end zone the filling of the material to be treated contained in the furnace chamber. A second electrode is arranged at the base of the chamber from the oven. When an electrical voltage is applied to the electrodes, an electrical current passes through the material introduced into the oven, which is heated in this way. The gas that is generated in this connection, which is in particular H ² and CO, is extracted from the furnace through openings. The resulting residual products in the form of fly ash or loose pyrolysis coke are removed through an opening in the bottom of the furnace.

Furthermore, from US 2008/256852 A1 a multi-stage oil refining process is known in which a mixture of coal and oil is coked in a second refining stage. To do this, the mixture of coal and oil is introduced into a delayed coker and heated. In this regard, a carbon product is generated as a by-product which must be suitable for use as an anode in the manufacture of aluminum. Further details on how the coking process is carried out are not disclosed in this connection.

Finally, document US 4,106,996 A discloses a process for improving the mechanical strength of coke in which a mixture ("liquor") of finely ground coal and oil with an oil content of 5-30% by weight is formed first in briquettes at 100 °C and then in round pellets. These pellets are introduced into a coking oven where they are charred under the influence of a hot gas stream passing through the pellets through openings in the base of the oven.

Starting from the state of the art previously exposed, the objective has been established of presenting a procedure with which a coking product can be economically manufactured that, due to its high density, can be used for direct use in the production of metals. , metal alloys and metallurgical products or as an intermediate product for the manufacture of the corresponding graphite elements whose properties meet the highest requirements.

The invention has achieved this objective by means of the method indicated in claim 1.

Advantageous embodiments of the invention are indicated in the dependent claims and explained in detail below, as well as the general concept of the invention.

The process according to the invention for the manufacture of a coking product consequently comprises the following work steps:

a) provision of a container enclosing an interior space and comprising a filling opening for filling a fluid or pourable carbon-bearing material into the interior space, as well as heating equipment for heating the filled carbon-bearing material into the interior space of the container;

b) introduction of the carbon-bearing material through the filling opening into the interior space of the container, the carbon-bearing material comprising a coking carbon component, as well as, optionally, solid carbon components in particular coking and, also optionally , additives that serve to adjust the properties of the carbon-bearing material;

c) heating the carbon-bearing material filled into the interior of the container by means of the heating equipment to a coking temperature, the heated carbon-bearing material being kept at the corresponding coking temperature in each case at the coking temperature until the carbon-bearing material maintained at the coking temperature solidifies by coking into the coking product;

- taking place, during the working step c), a relative movement oriented along the longitudinal axis of the container between the carbon carrier material heated in each case and the heating equipment,

- the heat emitted by the heating equipment covering in each case only a partial volume - which extends over a certain partial section of the height of the interior space of the container - of the carbon-bearing material filled in the interior space,

Y

- or the carbon carrier material filled into the interior of the container remains stationary while the heating zone moves from the base arranged below in the direction of gravity in the opposite direction of gravity towards the upper end of the container ,

either

- the heating equipment is arranged stationary and the carbon-bearing material filled in the container is moved relative to the heating equipment, either the container with the carbon-bearing material filled inside it moving along the stationary heating equipment or being provided in the base of the container a discharge opening by means of which the coking product is continuously withdrawn from the container as a filament formed by the respectively solidified carbon-bearing material (working step e)); Y

d) the gas that escapes from the carbon-bearing material during heating and holding is discharged from the container (step c));

e) extraction of the coking product out of the vessel.

In order to further refine the coking products made according to the invention, by completing the work steps a) - e) necessary according to the invention, in particular to increase the quality of the graphitized products, they can also be optionally traversed in each case the following work steps after work step e):

f) cooking of the coking product;

g) impregnation of the coking product with a carbon-based liquid filler and subsequent refiring of the impregnated coking product;

h) production of a graphite product by graphitization of the coking product.

Unlike conventional processes, in which a granular starting product is used which is converted into a moldable mass by mixing with a binder to form a green compact which is then subjected to a coking treatment, the process according to The invention is based on an initial fluid product, specifically a carbon-bearing material, whose essential component is a liquid or liquefiable carbon carrier, the carbon-bearing material also containing solid carbon components and other solid or liquid components (additives). without losing in this respect, however, its fluid character.

In this regard, used as additives are, for example, iron oxide or titanium oxide to reduce the swelling effect, a source of boron, such as pure boron or boron carbide, to improve the crystal structure and thus reduce the coefficient of thermal expansion, or carbon or graphite fibers, which contribute to improving the mechanical properties and also to reducing the coefficient of thermal expansion.

To manufacture a coking product whose mechanical, thermal and electrical properties meet the most demanding requirements, a carbon-bearing material is used, therefore, a carbon-rich and coking product that is already liquid at room temperature or that is brought to a fluid state by heating and subsequent melting, but which is in any case liquid during the coking process.

The carbon-carrying materials used according to the invention usually come from heavy fraction petroleum processing, such as petroleum distillation residues, coal tar derivatives, liquid phase pyrolysis (other fluid organic components) . The use of products from biomass processing, such as cellulose, sugar or starch, is also conceivable. In this connection, the aforementioned materials are only indicated here by way of example. Of course, other carbon-containing substances that are present in liquid form or in a form that can be melt-liquefied and coked can also be used for the purposes according to the invention. Correspondingly, the fluid or liquefiable carbon component of the carbon-bearing material consists in particular of at least one component from the following group: "Residues from petroleum distillation and coal utilization, such as tars and their derivatives, pitch, fluid bitumen, resins and biomass transformation products, such as cellulose, sugar and starch".

As a solid carbon component, at least one component from the following group may be present in the carbon-bearing material used according to the invention: "coke present in granular form, coal, bitumen in solid form, lignites, anthracite coal, graphite , substances from the recycling of carbon fibres", these materials also being mentioned only by way of example and being able to be used for the purposes according to the invention, of course, also other carbon-containing residues that are present in solid form and can be coked.

The chars made according to the invention can be used directly as carbon providers for applications where they serve as reaction partners or electrodes for chemical and electrochemical reactions. An important field of application in this case is the use in installations for the manufacture of aluminum in which the coking products produced according to the invention can be used as anodes or cathodes, in particular as anodes without having to undergo further processing steps. work to change its structure or density.

If higher mechanical, electrical and, in particular, thermal requirements are placed on the coking products according to the invention, the optional working steps f) - h) already mentioned above can be completed after working steps a). - e) of the process according to the invention. In this way, the coking products generated according to the invention can be used as an intermediate product for the manufacture of high-quality graphite elements, such as those required, for example, as electrodes in the foundry or metallurgical treatment of steels. in an electric steel mill.

By using the invention as a starting product a carbon carrier material consisting of predominantly liquid or liquefiable components, it is possible to produce a coking product with low porosity. In this sense, the procedure according to the invention ensures that as few gas bubbles as possible remain trapped in the resulting coking product. The dimensions of the container that determine the shape of the coking product produced according to the invention can be selected in this respect in such a way that they correspond to the final dimension adapted to the respective intended purpose, if necessary, taking into account any machining allowances that may be necessary.

The container provided according to the invention can be made of a sufficiently temperature-resistant steel sheet, in a manner known per se.

In order to facilitate in work step e) the removal of the finished coking product from the container, the container can be covered with a sliding layer at least in sections on its inner surfaces surrounding the interior space of the container. To do this, a separately prefabricated liner that fits tightly to the inner surface of the container can be introduced into the interior space of the container, or a liner made of a suitable material can be applied directly to the inner surface in question. As a material for the sliding surface, a light metallic material, in particular an aluminum material, but also a thin sheet of steel, comes into consideration.

In work step b) of the method according to the invention, the fluid carbon carrier material is introduced into the interior of the container through the filling opening of the container. In this connection, the filling opening can be formed by a filling tube or the like which is guided through a cover, a wall or a lid of the container into the surrounding interior space.

In order to increase the fluidity of the liquid or fusible carbon component given to the container according to the invention, it may be convenient to preheat the carbon component itself or the entire carbon-bearing material before filling it into the interior space of the container. In this case, the preheating is preferably carried out in such a way that the meltable carbon component which may be present and attributable to the liquid component is already liquefied when it enters the container. However, the heating can also be carried out in the vessel in such a way that an optimum liquid state of the carbon-bearing material is first established and then the coking process begins.

According to a first variant, the filling can be carried out in such a way that the entire amount of carbon-bearing material to be coked is first filled into the container (step b)) and only after filling is brought to heating to the coking temperature and holding at the coking temperature (step c)) is carried out, i.e. heating of the carbon material only starts after filling of the carbon-bearing material has been completed (working step b)).

According to a second variant, it is also possible to start already with the heating of a partial volume filled in the container with the total amount of carbon carrier material required (operation step c)) for the production of the coking product while further filling more carbon-bearing material in the inner space (work step b)).

While the first variant allows simplified process management, the second variant allows the production of particularly dense and high-quality coking products with minimized porosity.

The coking temperatures established according to the invention during the coking process (working step c)) are normally 450 - 900 °C, coking temperatures of at least 600 °C being able to safely achieve complete in the technical sense within a practical coking period, even for large volume coking products.

Simultaneously, by setting the coking temperature in the range of 450 - 900 °C, it is ensured that sufficiently fluid carbon-carrying material is always available during the process to automatically fill the pores created by the degassing processes in the respective partial volumes of the carbon-bearing material being carbonized in each case with flowing carbon-bearing material. The fluid carbon carrier material, which fills the openings and cavities left by the gas inevitably produced during coking, ensures according to the invention an optimally high density of the coking product obtained.

In this connection, it has been shown that in the process according to the invention the electrical conductivity of the products produced according to the invention can be directly influenced by adjusting the coking temperature. Thus, electrical conductivity increases with increasing coking temperature. Therefore, by setting high coking temperatures, electrical conductivities can already be achieved in the coking product produced according to the invention, which allow direct graphitization or other direct use of these products after the coking process according to the invention. . Thus, they can be used, for example, products made according to the invention directly as anodes or cathodes, in particular as anodes, in aluminum production.

With a coking temperature of at least 650 °C, in particular at least 700 °C, a further significant reduction in electrical resistance occurs, resulting in optimally low resistances of 10-50 Ohm and an associated optimum electrical conductivity at temperatures coking temperature of at least 800 °C. In this respect, a longitudinal graphitization of the coking product can already be achieved in the course of the process according to the invention by a suitable setting of the coking temperature, which is usually at least 800°C.

At a coking temperature higher than the upper limit of 1200 °C, the conductivity no longer improves, so that the coking temperature range can be practically limited to at most this upper limit.

In order for as few gas bubbles as possible to be trapped in the coke, the invention provides for a suitable temperature and flow regime, in particular when passing through the temperature range of 450 - 600 °C, to

a) ensure that there is a sufficient quantity of liquid carbon carrier material to guarantee the automatic filling of the created pores,

b) at the same time, keep the amount of liquid carbon carrier material as low as possible to favor degassing and the elimination of the gas bubbles that form,

c) allow the coking process to run quickly and

d) to avoid spontaneous coking and consequent "freezing" of the gas bubbles.

The coking time during which the carbon-bearing material is kept at the respective coking temperature depends directly on the heated volume in each case. In any case, the coking time must be calculated in such a way that in each case the carbon-bearing material kept at the coking temperature is fully baked in the technical sense at the end of the coking time. The coking time depends on the volume to be baked and, in the case of successive filling, on the progress of the filling process. Typical coking times for large-volume coking products, such as electrodes, are in practice between 6 h and 96 h. When making coking products with smaller volumes or small cross sections, the coking time can also be less than one hour.

In order to increase the flow of the gas generated during coking out of the carbon-bearing material, the atmosphere present in the interior space of the container can be sucked off. In this way, in the inner space of the container, above the carbon-bearing material filled in it, a negative pressure is generated, which can go up to a vacuum. A suitable absolute pressure for this is in the range from 1 to 50 hPa.

The manner of filling the mold (working stage b)) and heating (working stage c)) can be selected in the process according to the invention depending on the requirements that are made of the density distribution of the product. coker manufactured according to the invention. For example, if there is a requirement of maximum density in the outer edge areas of the coking products in a sufficient thickness and, on the contrary, a certain residual porosity is accepted in the central core area, it may suffice if a piece of equipment stationary heating, which detects the total volume of fluid carbon carrier material filled in the container, is arranged in a stationary container. In this case, the coking process proceeds starting from the edge zone of the carbon-bearing material adjacent to the inner surface of the container, which is captured first and foremost by the heat generated by the heating equipment, in the direction of the core zone of the carbon-bearing material. The gas bubbles created during the coking process can escape in this connection through the core zone of the carbon-bearing material, which remains liquid for a longer period of time. At the same time, the liquid carbon carrier material flows out of the liquid core zone into the pores left by the gas bubbles in the already fired edge region in each case, so that a zone of edge of optimal density and considerable thickness. Only in the last stage of coking, in particular when the central nuclear zone is also coking, can gas bubbles be trapped in them. However, the diameter of the core zone affected by the porosity thus caused is so small compared to the thickness of the optimally dense edge layer of the coking product thus produced according to the invention that it is negligible in applications such as, for example, , electrodes for reduction furnaces.

A minimized porosity in the entire cross section of the coking product manufactured according to the invention and an optimized density associated with it can be achieved by taking place during the working step c) an aligned relative movement along the longitudinal axis of the mold in each case between the heated carbon carrier material and the heating zone generated by the heating equipment. This relative movement can be continuous or gradual. In the case of a continuous relative movement, the speed of this movement can also vary depending on the coking progress of the carbon-bearing material. Similarly, in the case of a gradual relative movement in which the heating zone or the container remain in each case for a certain time in one position until the heating zone or the container moves to the next position, the time of exposure to heat of the volume of carbon-bearing material covered in each case by the heating zone can be controlled by adjusting the residence time.

By moving the heating zone with respect to the carbon-bearing material or the carbon-bearing material with respect to the heating zone, it is possible to make the coking process not only progress, as in the previously explained variant of the process according to invention, from the outer edge to the central core zone of the volume of the carbon-bearing material filled into the inner space of the container which in each case encompasses the heating equipment, but at the same time also in the direction of relative movement. In this way, a uniform increase in the coked volume can be achieved in each case of the carbon-bearing material over the entire cross-section, thus ensuring that a high density is also present in the core zone of the coked product obtained according to the invention. .

According to a first variant of this design of the method according to the invention, the heat emitted in the heating zone by the heating equipment covers in each case only a partial volume - which extends over a certain partial section of the height of the inner space of the container - of the carbon-bearing material filled in the inner space, the carbon-bearing material filled in the inner space being stationary during heating (working step c)), whereas, on the contrary, the heating zone generated by the respective heating equipment moves from the base arranged below in the direction of gravity in the direction opposite to the direction of gravity towards the upper end of the container. Gas bubbles escaping from the partial volume, heated by the heating equipment to coking temperature, of the carbon-bearing material contained in the inner space of the vessel, in this design can escape upwards against gravity through the carrier material. of fluid carbon, which comes out above the partial volume of the carbon-bearing material found in each case in the coking process (working stage c)) and is covered by the heat of the heating equipment, while at the same time, due to the effect of gravity, the liquid carbon carrier material pushes with gravitational pressure towards the openings and cavities left by the gas bubbles in the already baked carbon carrier material and fills them, so that a product of overall dense and largely poreless coking.

In this connection, it is particularly advantageous that, in the method according to the invention, the filling of the container and the heating of the volume of carbon-bearing material contained in each case in the container can temporarily take place at the same time. In this way, the amount of fluid carbon-bearing material that is above the partial volume covered in each case by the heat of the heating equipment during the coking process can be controlled in such a way that, on the one hand, the distance traveled by gas bubbles through the still liquid carbon-bearing material is optimally short, but, on the other hand, the column of fluid carbon-bearing material weighing on the already coked carbon-bearing material is so large that there is always a sufficient amount of fluid carbon-bearing material above the partial volume of already coked carbon-bearing material and, optimally, the thrust of the fluid carbon-bearing material in the pores of the already coked carbon-bearing material is reinforced by the material's own weight carbon carrier still liquid.

In the case of a stationary mounted container, the relative movement between the heating zone and the carbon-bearing material contained in the container can be achieved by moving the heating equipment that generates the heating zone along the container.

Alternatively, however, it is also possible to provide a stationary heating device which extends over the entire length of the volume filled in the carbon carrier material container and which is divided into several heating segments in the longitudinal direction of the container. Thus, these can be activated and deactivated consecutively so as to achieve a continuous or gradual movement of the heating zone generated by the heating segments of the heating equipment along the container.

In another first variant of the method according to the invention, the heat emitted in the heating zone by the heating equipment also covers in each case only a partial volume - which extends over a certain partial section of the height of the interior space of the container - of the carbon-bearing material filled into the interior, the heating equipment being arranged in this case, however, stationary, while the carbon-bearing material filled in the container moves relative to the heating zone generated by the heating equipment. Basically, for this the container with the carbon carrier material filled in it can be moved along the stationary heating equipment.

However, in a particularly productive design of this process variant based on stationary heating equipment, which additionally results in optimally formed coking products, the vessel is mounted in a stationary position, an opening of discharge by means of which the coking product is continuously withdrawn from the vessel as a filament formed by the respectively solidified carbon-bearing material (working step e)). In this design, the container is configured in the manner of a casting mold. Simultaneously, the heating equipment is mounted in the vessel in such a way and the discharge rate with which the filament-finished coking product is drawn continuously from the vessel is selected such that the carbon-bearing material filled in the container in the fluid state is completely coked in the technical sense on its way to the discharge opening and correspondingly solidifies. In addition to the increase in productivity, there is also the particular advantage in this case that the volume of fluid carbon-bearing material, which is in each case in the container above the already coked partial volume of carbon-bearing material, can be adjusted. in such a way that, on the one hand, the distance that the gas bubbles escaping from the partial volume found in the coking process (work stage c)) must travel is short and, on the other hand, there is always enough liquid carbon-bearing material to fill the pores left by gas bubbles in the already coked carbon-bearing material. The coking product drawn from the vessel in filament form may optionally be cooled at an accelerated rate to allow rapid post-processing. From the coking filament obtained, coking products of the desired length can be cut in each case.

In the embodiment variants in which a relative movement takes place between the carbon carrier material and the heat source, the speed of the relative movement depends on the diameter or the cross-section of the product to be manufactured. In this connection, the speed decreases proportionally with the increase in diameter or cross-sectional size due to the volume of carbon-bearing material covered in each case by the heating zone for the coking process. When generating cylindrical electrodes with the usual diameters in practice, the speed of the relative movement between the heating zone and the carbon-bearing material contained in the container is usually in the range of 0.025 - 1.5 m/h, in particular 0.05 - 0.5m/hr.

The degassing (work stage d)) of the gas that escapes from the carbon-bearing material found in the coking process (work stage c)) can be assisted by setting the carbon-bearing material contained in the container in motion, by least temporarily. For this, it is possible to provide, for example, vibration equipment or the like that excites the carbon-bearing material contained in the container so that it vibrates as a whole or in certain areas, ideally in the range of 0.5 Hz to 50 kHz. .

The heating equipment used according to the invention to heat the carbon-bearing material can be designed in such a way that it generates a certain temperature profile within the carbon-bearing material contained in the container and covered in each case by the heat of the heating equipment. . Thus, in particular in process variants in which a relative movement takes place between the heating zone generated by the respective heating equipment and the carbon-bearing material, it can be useful, for example, to operate the heating equipment in such a way that the new partial volume of carbon-bearing material entering the action zone of the heating equipment in each case is slowly brought to the respective coking temperature, i.e. that the heating power acting on the respective partial volume of material carbon carrier increases the more between the respective partial volume in the effective zone of influence of the heating equipment and the longer it is exposed to the heat emitted by the heating equipment.

The process according to the invention produces coking products which already during coking obtain the geometry close to the final dimension. Thus, the conventional work steps in the manufacture of coke preparation, mixing, shaping and first firing electrodes are eliminated and the possibility of also dispensing with impregnation and a second firing of the coking product manufactured in accordance with the invention for the production of a fully graphitized final product. Thus, the process according to the invention provides a coking product of high strength and density already without impregnation. This is characterized by having an average density of at least 1.4 g/cm3, densities of at least 1.5 g/cm3 being regularly achieved.

As a monolithic structure is made in the process according to the invention, close to the final dimension, already in the coking process, it is characterized by its high mechanical resistance. Furthermore, the spatial expression of the physicochemical properties of the coke can be controlled by the selective application of heat. In particular, a high electrical conductivity in the longitudinal direction and a low coefficient of thermal expansion can thus be achieved.

In the following, the invention is explained in more detail by means of a drawing showing an exemplary embodiment. They show in each case schematically:

Figures 1a-1d a first device for the production of a coking product in four equally spaced temporally spaced operating times, in each case in a section along the longitudinal axis of the device;

Figures 2a-2d a second device for the production of a coking product in four equally spaced temporally spaced operating times, in each case in a section along the longitudinal axis of the device;

Figure 3 a third device for the production of a coking product in a section along the longitudinal axis of the device;

Figure 4a a fourth device for the production of a coking product in a process not according to the invention in a section along the longitudinal axis of the device; FIG. 4b shows a coking product produced in the device shown in FIG. 4a in a longitudinal section.

The device 1 for the manufacture of a coking product VK shown in figures 1a-1d comprises a container 2 with its longitudinal axis L aligned vertically and formed in the style of a cylindrical tube which is made of a heat-resistant material, such as a commercially available steel for this purpose. The container 2 encloses an interior space 3 which widens in the form of a funnel in an upper section 4 towards the upper edge of the container 2.

The fine cylindrical shape of the interior space 3 is chosen so that the coking product VK produced in device 1 has an equally fine cylindrical shape at the end of the completed coking process in device 1 that optimally approximates the shape it should have the VK coking product or the graphite product made from it. In this regard, the dimensions of the VK coker may comprise a machining allowance that is required for subsequent machining to give the VK coker or a graphite product made therefrom its required dimensional accuracy or surface finish. Thus, in this case, the cylindrical shape represented by the interior space 3 of the container 2 corresponds in its design and dimensions to the shape that the graphite electrodes must have in order to be used in electric arc furnaces in steel mills. Likewise, the shape of the interior space 3 can be used to reproduce other shapes of coking products, such as, for example, blocks formed by coked carbon-bearing materials or the like. Thus, its shape can be optimally adapted to the conditions of the aluminum manufacturing facilities, for example, if necessary, also including the machining margin required in each case.

The inner surfaces of the container 2 delimiting the interior space 3 can be covered as a dividing layer at least in sections with a thin sliding layer 5 consisting, for example, of an aluminum material that is applied in the form of a prefabricated lining inserted into the space interior 3 or by means of a suitable coating method in a manner known per se directly to the relevant sections of the interior surfaces.

The opening present in the upper part of the container 2 is closed by a removable lid 6.

A filling tube 7 for filling the interior space 3 of the container 2 with a fluid carbon carrier material K is guided through the lid 6.

Additionally, a suction tube 8 is led through the cover 6, which is connected to an evacuation equipment that is not shown in this case and through which a negative pressure can be generated in the interior space 3 to suck in the gases present. in the inner space 3.

With its lower part, the container 2 rests on a base element 9 which closes the container 2 on its lower side.

The device 1 also comprises an electrical and adjustable heating equipment 10 that is placed with its heating coils 11 in an annular shape and with clearance around the outer surface 12 of the container 2. The height H10 of the heating equipment 10 corresponds to a small fraction of the height H3 of the interior space 3 of the container 2. For example, the height H3 can be up to 15 m, while the height H10 is usually only 1 m.

The heating device 10 is supported by an adjustment device 13, which is designed in a manner known per se to move the heating device 10 in the vertical direction V along the container 2. For this, the adjustment device 13 can have a linear guide. 14 aligned axially parallel to the longitudinal axis L, along which the heating device 10 can be moved by means of a linear drive 15 of the adjusting device 13.

The device 1 further comprises equipment 16 which is intended to apply the fluid carbon carrier material K contained in the interior space 3 of the container 2 with vibrations in the range of 0.5 Hz to 50 kHz. In order to achieve the strongest possible effect on the in each case still fluid and uncoked volume of the carbon carrier material K, the vibration device 16 can also be supported by the adjusting device 13 and moved during the coking process with the heating equipment 10 along the container 2. In this regard, the vibration equipment 16 is preferably located above the heating equipment 10 in order to cause the most optimal effect possible of the movement generated by it in the still fluid carbon-carrying material K .

To manufacture a column-type coking product VK, the inner space 3 of the vessel 2 is filled with fluid carbon-bearing material K through the filling pipe 7 until the level SK of the carbon-bearing material K contained in the inner space 3 is approximately in the transition zone between the funnel-shaped upper section 4 and the underlying cylindrical part of the interior space 3.

The heating equipment 10 is placed in an initial position at the lower end of the container near the base element 9, during the filling process.

After the container 2 has been filled with the fluid carbon-bearing material K, the heating device 10 is actuated, for example with electrical energy, so that the partial volume of the carbon-bearing material K present in each case in the area of influence of the heating zone generated by the equipment heater 10 is gradually raised to a coking temperature of 450 - 900 °C, in particular 650 - 850 °C. As a result of the heating, decomposition processes are initiated in the thus heated partial volume by means of which gases still contained in the fluid carbon-bearing material K are released, which rise in the form of gas bubbles G in the carbon-bearing material K. against the direction of action SR of gravity. The space released by the decomposition processes in the carbon-bearing material K is replaced by the fluid carbon-bearing material K from the column of carbon-bearing material present in the inner space 3 of the container 2, which automatically pushes forward as a result of the effect of gravity. This process continues until the partial volume heated in each case by the heating device 10 in the heating zone it generates has been completely coked in the technical sense and has assumed a solid form. Since all the cavities that have become free due to gas formation have been immediately filled in each case by the buoyant carbon-bearing material K, the density of the thus coked partial volume of the carbon-bearing material K is at least 1 .4g/cm3.

The detachment of the gas bubbles G from the carbon-bearing material K is, on the one hand, mechanically reinforced by the vibrations that are induced by the equipment 16 in the carbon-bearing material K. On the other hand, the extraction of the bubbles The release of gas G from the carbon-carrying material K is promoted by maintaining a negative pressure in the interior space 3 of the container 2 through the suction tube 8, which can go up to vacuum.

Since coking occurs by symmetrical heating of the sides of the interior space, coking proceeds from outside to inside. During coking of the outer layer, both in the core zone and in the layer above it, there is liquid and initially low-viscosity carbon-carrying material K through which gas bubbles G can escape and thus close possible pores. This allows a high density of the coking product obtained. During coking of the core zone, carbon bearing material K can flow from the upper layer. In this case, too, the pores are thus closed.

If, despite this, small gas bubbles remain trapped in the core zone KB of the coking product VK, this has only a slight influence on the mechanical properties, since the neutral axis of the coking products VK in each case with Columnar shape runs along the core zone in question and, therefore, this zone is not subjected to high tensile or compressive stresses during use.

After the partial volume of the carbon-bearing material K adjacent to the base element 9 has been coked, the heating device 10, which is still in heating mode, and with it the vibration device 16, which is also still active, are moved by means of the adjustment equipment 13 against the direction of action SR of gravity by means of the linear drive 15 in a continuous movement along the linear guide 14 in the direction of the upper end of the container 2.

The speed of the upward movement of the heating device 10 and of the vibration device 16 coupled to it is dimensioned in such a way that the partial volume of the carbon-bearing material K which is in each case in the zone of influence of the zone generated by the heating equipment 10 is gradually heated and then maintained at the respective coking temperature for a coking time sufficient for complete coking in the technical sense and associated complete solidification. In practice, for this, transport speeds of the heating equipment 10 are generally envisaged in the range of 0.025 - 1.5 m/h, in particular 0.05 - 0.5 m/h.

The movement of the heating equipment 10 is maintained until also the upper section of the carbon-bearing material K adjacent to the level SK of the carbon-bearing material K has coked. The level SK of the carbon-bearing material K in this connection has dropped with respect to the just-filled state of the interior space 3 of the container 2 due to the gas that has escaped from the carbon-bearing material K and the concomitant loss in volume.

After the upper zone BP of the carbon-bearing material K adjacent to the level SK is also coked and has assumed a solid form, the vessel 2 is opened and the coking product VK formed in the inner space 3 is withdrawn from the inner space 3 The sliding coating or layer 5 present on the inner surfaces of the container 2 adjacent to the inner space 3 facilitates in this respect the extraction of the coking product VK.

If it becomes apparent that the required density of at least 1.4 g/cm3 has not been reached in the upper region BP of the coking product VK, because there is no longer enough available carbon-bearing material K at this location during coking to fill the gaps left by the gas bubbles G that form, the LP zone in question is separated. It can be recycled for reuse by grinding into fine particles which can be added to carbon carrier material K as solid carbon components which are provided for the manufacture of other coking products VK in device 1.

The coking product VK thus obtained is subjected for the manufacture of a graphite electrode such as is required in an electric steel plant, to a conventional graphitization process to give it a graphite structure. Due to the monolithic geometry, close to the final dimension, already obtained with device 1 in the manner described above after the first coking, the grinding, mixing and shaping processes usual in the conventional procedure are as obsolete as the corresponding initial firing. Depending on the achieved density of the product, the impregnation step can also be omitted. If it turns out that the density of the obtained coking product VK is not sufficient, the impregnation can also be carried out in a conventional way to increase the density before the coking product VK is transformed into the graphite product, that is, into the graphite product. graphite electrode.

The device 101 shown in figures 2a - 2d for the production of a coking product VK corresponds in its construction to the device 1 shown in figures 1a - 1d, with the difference that in the device 101, instead of the coking tube fixedly mounted filling tube 7 provided in the device 1, a lance-shaped filling tube 107 is provided which can be inserted into the inner space 3 of the container 2 of the device 101 and withdrawn therefrom. The maximum insertion length of the filling tube 107 is dimensioned in this respect in such a way that the filling tube 107, when completely inserted in the interior space 3, ends just above the height H10 to which the zone extends. of heating generated by the heating equipment 10 in the initial position of the heating equipment 10 (figure: 2a). In this way, the negative effects of splashes that can occur during the coking process are avoided.

To manufacture a column-type coking product VK in the device 101, the inner space 3 of the vessel 2 is filled with a partial volume of fluid carbon-bearing material K through the filling pipe 107 until the level SK of the carbon-bearing material carbon K contained in the interior space 3 ends above the height H10 to which the heating zone generated by the heating equipment 10 extends in its initial position (figure 2a).

Next, this partial volume of the carbon-bearing material K that forms the lower section of the coking product VK to be manufactured is gradually and controlled brought up to the coking temperature in device 1.

With the start of coking, more fluid carbon carrier material K, preheated for liquefaction if necessary, is supplied almost continuously through the filling tube 107, which is raised by a corresponding amount in height, and the equipment The heater 10 with the vibration equipment 16 attached to it is moved along the container 2 by means of the adjustment equipment 13 in the manner already described for the device 1. The movement of the filling tube 107, which can be adjusted in height by means of an adjusting device, not shown here, and of the heating device 10 are coordinated with each other in this respect in such a way that the vertical distance between the heating device 10 and the free end of the filling tube 107 projecting into the carrier material carbon K remains constant. In this regard, the free end of the filling tube 107 always remains close to the level SK of the carbon carrier material K filled in the container until the maximum filling level of the container 2 is reached.

The height of the level SK of the carbon-bearing material K is maintained in this respect in such a way that a sufficient amount of fluent carbon-bearing material K is always available above the partial volume of the carbon-bearing material K in the coking process to filling the voids left by the gas bubbles G emerging from the partial volume of the carbon-bearing material K heated to the coking temperature and maintained at the coking temperature. The distance that the gas bubbles G have to cross in this connection through the fluid carbon carrier material K is shorter than in the device 1, so that an even more optimized density of the coking product VK can be achieved.

Fig. 3 shows a device 201 for the production of a coking product VK in which, unlike devices 1 and 101, a heating equipment 210 provided in device 201 is mounted stationary, i.e. it remains stationary during heating. operation, while the carbon-bearing material K which is already to be coked moves along the heating equipment 210 and is coked on this path along the heating equipment 210 into a solid coking product VK which is continuously withdrawn from the device 201 in the manner of a continuous casting process.

The device 201 has a container 202 for this purpose that delimits an internal space 3 which, like the internal spaces 3 of the devices 1,101, widens in the shape of a funnel in an upper area and is closed with a lid 206. In this case, as also in that of the covers 6 of the devices 1,101, a suction tube 208 and a filling tube 207 arranged in the manner of the filling tube 7 of the device 1 are guided through the cover 206.

The cylindrical area 217 of the interior space 203 arranged below the funnel-shaped upper area is designed to be open downwards in the manner of a mould, and is considerably shorter than in the devices 1, 101. The section surrounding the area 217 of the container 202 sits in this connection on the annular-shaped heating device 210 which extends over a substantial part of the height of the area 217. In this connection, the heating coil 211 of the heating device 210 can be adjusted in segments to allow a profile of temperature in the respective partial volume of the carbon-bearing material K located in each case in the area of influence of the heating zone generated by the heating equipment 10.

For the production of a coking product VK, the lower outlet opening of the mold-like zone 217 of the interior space 203 is first closed with a plug and a first partial volume of carbon-bearing material is filled. carbon K into the interior space 203 of the container 202 through the filling tube 207.

By means of the stationary heating equipment 210, the carbon-bearing material K in the area of influence of the heating zone generated by the heating equipment 210 is gradually controlled, heated to coking temperature, and kept there until is fully coked in the technical sense and has acquired a solid form.

In the course of the coking process, the carbon-bearing material K coked in this way is continuously drawn from the mold-shaped area 217 of the inner space 203 of the container 202 as a filament by means of the plug through its lower opening. At the same time, the optionally preheated new carbon carrier material K is also continuously filled into the container 202 via the filling tube 207. The lower opening area 218 of the area 217 can be enlarged by funnel-shaped in the direction of gravity SR to facilitate extraction of the filament-shaped coking product VK. The extraction forces are dimensioned in this respect in such a way that the coking product is continuously extracted from the vessel 202 despite the negative pressure/vacuum present in the vessel 202 above the carbon-bearing material filled therein.

In this case, the extraction and filling process take place synchronously with one another, so that the residence time in which the carbon-bearing material K passes through the heating equipment 210 is kept at the coking temperature corresponds to the coking time required for complete coking in the technical sense.

As in the device 101, in this respect the height of the level SK of the fluid carbon carrier material K above the carbon carrier material K, which has already solidified as a result of coking, is adjusted in such a way that, On the one hand, the gas bubbles G emerging from the carbon-bearing material K encountered in coking only have to travel a short distance through the fluid carbon-bearing material K until they are sucked in after the carbon-bearing material exits. carbon K through the draft tube 208, but, on the other hand, a sufficient amount of fluid carbon-bearing material K is also always available to fill the pores left by gas bubbles G in the carbon-bearing material K being formed. solidifies with the pushing liquid carbon carrier material K. Even with a device of the type shown in figure 3 it is possible to manufacture optimally dense coking products and with an optimally homogeneous distribution of properties.

The degassing of the gas bubbles G can be assisted by vibrating equipment 216 which, as in the devices 1,101, is arranged above the heating equipment 210, but in this case, corresponding to the fixed arrangement of the heating equipment 210, it is stationary mounted. As already mentioned, in this respect the container 202, which functions as a mould, can also be applied with a negative pressure/vacuum in the area above the carbon-bearing material K which is inserted into it to enhance degassing. of the gases G of the carbon-bearing material K formed in the coking process in vessel 202.

The coking product VK drawn continuously in filament form from device 201 passes through a cooling leg 219 after exiting vessel 202 where it is cooled to room temperature in an accelerated process. Subsequently, in a cutting device 220, the coking products VK are cut from the filament to the desired length in each case in a manner known per se.

As in the case of continuous casting of molten metal, two or more of these mold-type vessel zones 217 with heating equipment 210 mounted on them in each case and vibrating equipment 216 also mounted on them, may be provided with a central collector, not shown in this case, which feeds the zones 217 of the mold-like container with carbon-bearing material K to achieve maximum productivity.

Figure 4a shows a device 301 for the manufacture of a coking product VK in a process not according to the invention comprising a pot-shaped container 302 made of a suitable steel material which is closed by a lid 306. A Through the lid 306, an extraction tube 308 is guided which is connected to a suction equipment not shown in this case in order to evacuate the interior space 303 surrounded by the container 302. The container 302 sits on a heating equipment 310 whose spiral The stationary and annular heating zone 311 extends over the entire height of the container 302, so that the heating equipment 310 can generate a heating zone correspondingly extending over the entire height of the container 302.

For the manufacture of a block-shaped coking product VK (FIG. 4b), the lid 306 of the container 302 is removed and the fluid carbon carrier material K is filled into the interior space 303 of the container 302. Thereafter, the container 302 is closed by placing the cover 306 and the carbon bearing material K contained in the container 302 is brought to a coking temperature of 450 - 900 °C. When the coking temperature is reached, coking and solidification of the carbon-bearing material K are started from the inner side surfaces of the inner space 303. In this regard, the core zone KB of the carbon-bearing material K remains highly fluid for a long time. period of time, such that the gas bubbles G arriving there, as well as the gas bubbles G escaping from the partial volumes of the carbon-bearing material K in the coking process, continue to move against gravity in the coking process. direction of the SK level of the carbon-bearing material K content in the container for a long time.

If the coking process has progressed so far that the KB core zone has also coked, this can cause smaller gas bubbles G to be trapped in the inner KB core zone. However, the porosity present there as a result is harmless, since coking products of the type made in the 301 device are commonly used for applications where the greatest demands are on conductivity and stability, in particular in the area of the outer edge sections of the coking product VK, while the quality of the core zone KB only plays a secondary role. These requirement profiles arise, for example, in aluminum production plants if VK coking products of the type produced according to the invention are to be used there as anodes or cathodes, in particular as anodes.

The fluid carbon carrier material K used in the devices 1, 101,201, 301 for the manufacture of the respective coking product VK consists in each case of products obtained during the distillation of petroleum products and the utilization of coal such as tars and their derivatives, pitch, fluid bitumen, resins and biomass transformation products, such as cellulose products, sugar and starch and other products that can be coked. This K-carbon carrier material is optionally mixed with granular coke or graphite with a maximum grain size of 10 mm and, if necessary, with one or more additives, such as iron oxide to reduce the swelling effect, a source of boron, such as boron carbide, to reduce the coefficient of thermal expansion or to improve the crystalline structure generated, or carbon or graphite fibers, which contribute to improving the mechanical properties and also to reducing the coefficient of thermal expansion. In this regard, the carbon carrier material K used in each case is liquid at the process temperature, in such a way that it flows under the effect of gravity towards the interior space 3, 103, 203, 303 defined in each case by the container 2, 102, 202, 302.

References

Figures 1, 2

1 Device

2 device container 1

3 Inner space of container 2

4 Upper section of interior space 3

5 slip layer

6 Container lid 2

7 Filler tube (filler opening)

8 Suction tube

9 Basic Element

10 Heating equipment

11 Heating coil of heating equipment 10

12 Outer surface of container 2

13 Adjustment Team

14 Linear guide of adjusting equipment 13

15 Linear drive adjustment unit 13

16 Vibration equipment

101 Device for the manufacture of a coking product

107 fill tube

BP Zone of carbon bearing material K adjacent to the SK level.

H10 Height of heating equipment 10

H3 Height of inner space 3

Figure 3

201 Device for the manufacture of a coking product

202 Container configured as a mold

203 Inner space of the container 202 configured as a mold

206 Lid

207 Filler tube (filler opening)

208 suction tube

210 heating equipment

211 Heating coil of heating equipment 210

216 Vibration Equipment

217 Cylindrical zone open towards the bottom of the interior space 203 of the container 202

218 Bottom area of enlarged funnel-shaped opening of zone 217

219 Cooling leg

220 cutting equipment

Figures 4a,4b

301 Device for the manufacture of a coking product VK

302 container

303 Inner space of container 302

306 Lid

308 suction tube

310 heating equipment

311 Heating coil of heating equipment 310

KB Core zone of carbon bearing material K

General

G Gas bubbles

K Fluid carbon carrier material

L Longitudinal axis of device 1

SR Direction of action of gravity

SK Mirror of the carbon carrier material K contained in each case in the interior space 3 of the container 2, 202, 302

VVertical direction

VK Coking product

Claims (10)

1. Process for manufacturing a coking product (VK) formed by solidifying a carbon-bearing material that is intended for use in the production of metals, metal alloys and metallurgical products or as an intermediate product for the manufacture of graphite elements and which presents a monolithic geometry close to the final dimension and a density of at least 1.4 g/cm3, comprising the following work stages: a) provision of a container (2,202), which - encloses an interior space (3) and - comprises a filling opening for filling the interior space (3) with a fluid carbon carrier material (K), as well as - a heating equipment (10,210) to heat the carbon carrier material (K) filled in the interior space (3) of the container (2,202); b) introduction of the fluid or pourable carbon-bearing material (K) through the filling opening into the interior space (3) of the container (2,202), the carbon-bearing material (K) comprising at least one coking carbon component fluid or meltable, as well as, optionally, at least one solid coking carbon component and, also optionally, at least one additive serving to adjust the properties of the carbon-bearing material (K); c) heating the carbon-bearing material (K) filled in the interior space (3) of the container (2,202) by means of the heating equipment (10,210) at a coking temperature, keeping the carbon-bearing material (K) heated at the corresponding coking temperature in each case at the coking temperature until the carbon-bearing material (K) held at the coking temperature solidifies by coking to give the coking product (VK), - taking place, during the working stage c), a relative movement oriented along the longitudinal axis of the container (2,202) between the carbon carrier material (K) heated in each case and the heating equipment (10,210), - the heat emitted by the heating equipment (10,210) covering in each case only a partial volume -which extends over a certain partial section of the height of the interior space (3) of the container (2,202)- of the carbon-bearing material (K ) filled in the inner space (3), and - or the carbon-bearing material (K) filled in the interior space (3) of the container (2, 202) remains immobile while the heating zone (10, 210) moves starting from the base arranged below in the direction of gravity in direction opposite to the direction of gravity towards the upper end of the container (2.202), either - the heating equipment is arranged stationary and the carbon-bearing material (K) filled in the container (2,202) is moved in relation to the heating equipment (10,210) moving either the container with the carbon-bearing material filled inside along along the stationary heating equipment or a discharge opening being provided at the base of the vessel (202) by means of which the coking product (VK) is continuously drawn from the vessel (2,202) as a filament formed by the carbon-bearing material (K) solidified in each case (working steps)); Y d) discharging from the container (2,202) the gas that escapes from the carbon-bearing material (K) during heating and maintenance (step c)); e) extraction of the coking product (VK) out of the vessel (2,202). 2. Procedure according to claim 1, characterized in that the fluid or fusible carbon component of the carbon-bearing material (K) is made up of at least one component from the following group: "Petroleum distillation residues, products resulting from the use from coal, tar and its derivatives, pitch, fluid bitumen, resins and biomass transformation products, cellulose products, sugar and starch". Method according to one of the preceding claims, characterized in that the carbon-bearing material (K) contains a solid carbon component consisting of at least one component from the following group: "coke present in granular form, coal, bitumen in the form solid, lignites, anthracite coal, graphite, products from the recycling of carbon fibers". Method according to one of the preceding claims, characterized in that the carbon-bearing material (K) contains an additive from the following group: "Iron oxide, titanium oxide, boron and boron compounds". Method according to one of the preceding claims, characterized in that the heating of the carbon-bearing material (K) (working step c)) only begins after the filling of the carbon-bearing material (K) has been completed (heating step). work b)). 6. Method according to one of claims 1-4, characterized in that the heating of the carbon-bearing material (K) (working step c)) begins while the carbon-bearing material (K) (working step b)) is filled in the inner space (3). Method according to one of the preceding claims, characterized in that the coking temperature in working stage c) is 450 - 900 °C. Method according to one of the preceding claims, characterized in that the coking time in operating stage c) is up to 96 hours. 9. Method according to one of the preceding claims, characterized in that the atmosphere present in the interior space (3) of the container (2,202,302) is aspirated to extract (work step d)) in a forced manner from the container (2,202) the gas that it escapes from the carbon-bearing material (K) heated to the coking temperature. Method according to one of the preceding claims, characterized in that the carbon-bearing material (K) is set in motion within the container (2,202) at least intermittently.