WO2020043314A1

WO2020043314A1 - Method for producing a coking product

Info

Publication number: WO2020043314A1
Application number: PCT/EP2018/073509
Authority: WO
Inventors: Max Aicher; Klaus Krüger; Andre Van Bennekom
Original assignee: Max Aicher Gmbh & Co. Kg
Priority date: 2018-08-31
Filing date: 2018-08-31
Publication date: 2020-03-05
Also published as: ES2915668T3; PL3810726T3; EP3810726A1; EP3810726B1; RU2762192C1

Abstract

The invention relates to a method for producing a coking product (VK), in which a container (2, 202, 302) is provided, which delimits an interior space (3) and comprises a filling opening and a heating device (10, 210, 310) for heating the carbon carrier material (K) filled into the interior space (3) of the container (2, 202, 302). The flowable or pourable carbon carrier material (K) introduced into the interior (3) via the filling opening is introduced into the container (2) via the filling opening, and comprises a liquid or fusible coking carbon component and optionally, a solid coking carbon component, and likewise optionally, an additive that serves to adjust the properties of the carbon carrier material (K). The carbon carrier material filled into the interior space (3) is heated to a coking temperature by means of the heating device (10, 210, 310), wherein in each case, the heated carbon carrier material (K) is kept at the coking temperature until by coking, the heated carbon carrier material is solidified to form the coking product (VK), wherein gas (G), which escapes from the carbon carrier material (K) during heating and holding, is discharged from the container (2, 202, 302). The coking product (VK) produced in this way is then removed from the container (2, 202, 302).

Description

Process for the manufacture of a coking product

The invention relates to a method for producing a coking product.

Coking products of the type produced and procured according to the invention are used, for example, as anodes in the production of aluminum or as electrodes in the melting 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

Manufacture of electrodes for the metallurgical treatment of metals or metal alloys can be found in the article "Graphite Electrode and Needle Coke Development" written by Rick Adams, Wilhelm Frohs, Hubert Jäger and Keith Roussel and published by the American Carbon Society in 2007 the URL http://acs.omnibooksonline.com/data/ papers / 2007_D031 (K) .pdf is available for download.

Accordingly, carbon is used in solid form, typically as coke, for the production of coking products of the type in question here.

provided. The coke is produced in the manner known per se, as a rule from residues which arise from the refining of petroleum or other petrochemical processes. Coking carbon carriers, such as residues resulting from the distillation of petroleum or comparable carbon carriers, become one

Subjected to coking process. Alternatively, coal tar pitch is used as a starting product for coking. Goes through if necessary the so-called green coke is a calcining process to remove the volatile hydrocarbons that are still present, especially in petroleum coke.

For applications in which the highest demands are placed on the mechanical resilience with minimized thermal expansion, such as, for example, in the melting or metallurgical treatment of steel in an electric arc furnace, so-called

Needle coke used. This represents the highest quality level and can only be produced with increased effort (DE 10 2004 035 934 A1). For applications in which there are less demands on the mechanical resilience or the thermal expansion behavior, the expensive needle coke can be partially or completely replaced by a cheaper type of coke or one of the other carbon carriers (e.g. anthracite coal).

The coke is ground into a pourable amount of grains, from which eight grain fractions are typically separated by sieving. Usually, coke of different grain fractions is mixed into a coke grain mixture with a grain size distribution which is considered to be optimal with regard to the properties of the graphite element to be set. Typically, mixtures are created which consist of a third of dust and two thirds of grain in order to ensure a sufficient density. It is assumed that the coke dust fills the gaps between the coke grains. Additives, such as iron oxide, can be added to the respective mixture. Iron oxide minimizes the irreversible thermal expansion of the coke ("puffing"), which occurs in the subsequent heat treatments when sulfur still present in the coke is driven out of the carbon lattice.

The one that is typically preheated to shorten process times

Grain mixture is mixed with a binder, such as tar pitch, Stearic acid or mixtures of these binders, mixed to a plastically deformable, pasty, homogeneously mixed mass, the binder content of which is typically 20-24% by weight. The carbon binder mass obtained, which is also referred to in technical jargon as “green mass”, is now shaped into a “green body” by pressing, extruding, shaking or stamping. During this molding process, the

Temperature below the mixing temperature, so that a tough, very highly viscous mass is present at this time.

The green compacts are then slowly heated to a temperature of typically 800 to 950 ° C. in the absence of oxygen. During this firing process, part of the binder decomposes into gas, which must escape from the green body. This gas development causes a slowly progressing heating, because otherwise the gas pressure developing in the green compact could lead to crack formation and the associated instability of the carbon or graphite element to be produced.

Depending on the binder system used, about a third of the mass of the binder used is lost during the firing process. The binder degassing from the green compact leaves voids in the intermediate product obtained after firing, as a result of which the intermediate product has a reduced density. As a rule, this is not sufficient for the production of carbon or graphite elements, of which high electrical conductivity and high strengths are required, such as for example

Graphite electrodes for steel melting or treatment. Therefore, the intermediate product obtained after the first firing is before

Further processing typically undergoes a so-called "impregnation". For this purpose, a heated impregnating agent, which has a lower viscosity than the binder originally used, typically tar pitch, is pressed into the intermediate product in order to fill pores present there. The intermediate product is then fired again. there In turn, part of the previously pressed-in impregnating agent evaporates, with the result that, even after an impregnating step, the intermediate product inevitably has open pores which are not filled with carbon.

Accordingly, the impregnation process must be repeated if necessary until the intermediate product has the density required for its further processing.

The intermediate product is subjected to a graphitization process for further processing to a graphite element of the highest quality. The carbon contained in the intermediate product is converted to graphite by heating to approx. 2800 ° C, which is characterized by an increasingly three-dimensional

Order of the carbon atoms. The so-called "Acheson process" or the more economical "Castner process", the so-called longitudinal graphitization (LWG), are usually used here. The lowest possible sulfur and nitrogen content of the raw material and the resulting reduced puffing tendency can support the process and success of the graphitization. The negative effect of nitrogen and sulfur still contained in the intermediate product can, as mentioned, also be reduced by suitable additives such as iron oxide or a targeted temperature control during the graphitization.

Processes based on the so-called “Söderberg process” (see, for example, US 1, 440.724 A, US 1, 640.735 A) avoid that in the production of graphite electrodes with the shaping of a green compact, with the burning of the green compact to an intermediate product and effort associated with the graphitization process.

In one embodiment of this method described in US Pat. No. 3,365,533 A, a pasty carbon carrier material, which consists of a mixture of granular coke and liquid tar distillate serving as a binder, is filled into a tubular housing of an electrode, which has one end in the furnace space of a reduction furnace ( Arc furnace) Melting / reduction of, for example, phosphorus, tantalum or

Ferromanganese is made from ores. The housing of the electrode is made of an electrically conductive carbon steel. A current is applied to the housing of the electrode, which is applied to the one filled in the housing

Carbon carrier material is transferred. In this way, an arc ignites in the furnace chamber, causing the temperatures in the region of the end of the electrode reaching into the furnace chamber to rise to more than 2000 ° C. As a result, the electrode contained in the housing

Carbon carrier material a temperature gradient through which the pasty

Carbon carrier material in the upper region of the electrode is kept molten at about 200 ° C. The temperature of the carbon carrier rises continuously in the direction of the end of the electrode assigned to the furnace space. The disintegrate in the temperature range from 400 ° C to 600 ° C

Carbon material containing hydrocarbon compounds. The gases released in this way should be able to escape in the direction of the upper end of the electrode protruding into the furnace space. At the same time, it should come from

Carbon derived from hydrocarbons fill the spaces between the coke grains. With increasing approach to the tip of the electrode protruding into the furnace chamber, this process continues until the carbon carrier material becomes a solid, compact body in the

Oven space protruding tip of the electrode has arisen. In the melting mode, the electrode is consumed and has to be pushed from above in order to maintain the arc in the furnace chamber.

In another variant of the described in DE 600 01 106 T2

Söderberg process is used in a furnace to melt one

Steel alloy also arranged an electrode with a cylindrical container, which is guided with its upper open end through the wall of the furnace. The container is made of a conductive stainless steel. The container is charged with a non-baked, lumpy electrode mass via its open upper end. On their way to the also open at the lower end of the container, the electrode mass is liquefied by the supply of heat, which takes place via heated air which is conducted in a central region around the container of the electrode, until it is in the region of a plate-shaped element which is positioned adjacent to the lower outlet opening of the container

Arrives for coupling an electrical current. As a result of the high temperatures prevailing in the area of the tip of the electrode reaching into the furnace space, the electrode mass is also burned “in situ” there. The solid electrode strand thus burned from the electrode mass is continuously fed from the lower outlet opening of the container into the

Furnace chamber promoted and serves as an electrode for the supply of electrical energy, via which the arc and thus the melting process in the furnace is kept going. The problem of ensuring a certain density of the graphite element produced in this way is also not addressed here, nor is the setting of certain mechanical or other properties which are important for the use of coking products with which the invention is concerned.

Starting from the prior art explained above, the task has arisen of naming a method which can be used to produce a coking product inexpensively, which due to its high density is suitable for direct use in the production of metals, metal alloys and metallurgical products or as an intermediate product can serve for the production of corresponding graphite elements, the properties of which are subject to the highest demands.

The invention has this object by the specified in claim 1

Procedure solved.

Advantageous embodiments of the invention are specified in the dependent claims and, like the general inventive concept, are explained in detail below. The method according to the invention for producing a coking product accordingly comprises the following working steps: a) provision of a container which delimits an interior and one

Filling opening for filling a flowable or pourable

Carbon carrier material in the interior and a heating device for heating the filled in the interior of the container

Includes carbon support material;

b) introducing the carbon carrier material via the filling opening into the interior of the container, the carbon carrier material comprising a liquefiable, coking carbon component and optionally solid, in particular coking carbon components and also optionally additives which are used to adjust the properties of the

Serve carbon carrier material;

c) heating the filled in the interior of the container

Carbon carrier material by means of the heating device on a

Coking temperature, the carbon carrier material heated to the respective coking temperature in each case for as long as

Coking temperature is maintained until the carbon support material is kept at the coking temperature by coking to the

Coking product is solidified and

d) wherein gas which escapes from the carbon support material during the heating and holding (step c)) is discharged from the container;

e) removing the coking product from the container.

In order to pass through those necessary according to the invention

Steps a) - e) refine coking products produced according to the invention, in particular the quality of the graphitized products increase, you can optionally also go through the following work steps after step e):

f) burning the coking product;

g) impregnating the coking product with a liquid

carbon-based filler and then re-firing the impregnated coking product;

h) creating a graphite product by graphitizing the

Coking product.

Unlike the conventional process, which uses a granular process

Starting material is used, which is converted into a moldable mass by mixing with a binder in order to form a green body, which is then subjected to a coking treatment, the process according to the invention starts from a flowable starting product, namely one

Carbon carrier material, the essential component of which is a liquid or liquefiable carbon carrier, the carbon carrier material also being able to contain solid carbon components and other solid or liquid constituents (additives) without, however, losing its liquid character.

Examples of additives used here are iron oxide or titanium oxide to reduce the puffing effect, a boron source, such as pure boron or boron carbide, to improve the crystal structure and thereby reduce the coefficient of thermal expansion, or carbon or graphite fibers to improve the mechanical properties and also contribute to reducing the coefficient of thermal expansion.

In order to produce a coking product whose mechanical, thermal and electrical properties meet the highest requirements, a carbon-rich, coking product that is already liquid at room temperature or by heating and thus is used as the carbon carrier material accompanying melting is brought into the flowable state, but in any case is liquid during the coking access.

The carbon carrier materials used according to the invention are typically obtained in the processing of petroleum from the heavy fraction, as residues in the distillation of petroleum, from coal tar derivatives, from liquid phase pyrolysis (other flowable organic components).

The use of products from the processing of biomass, such as cellulose, sugar or starch, is also conceivable. The above are

mentioned materials mentioned here only as an example. It can

Of course, other carbon-containing substances, which are in liquid or meltable form and can be coked, are used for the purposes of the invention. Accordingly, the liquid or liquefiable carbon component of the

Carbon carrier material, in particular from at least one component from the following group: "Residues from the distillation of petroleum and

Utilization of coal-based products such as tars and their derivatives, pitch, flowable bitumen, resins or products from the processing of biomass such as cellulose, sugar and starch ".

At least one component from the following group can be present as the solid carbon component in the carbon carrier material used according to the invention: “Granular coke, coal, bitumen in solid form, lignites, anthracite coal, graphite, materials from the recycling of

Carbon fibers ”, whereby these materials are only mentioned as examples and of course other carbon-containing residues, which are in solid form and can be coked, can be used for the purposes of the invention.

Coking products produced according to the invention can be used as

Carbon suppliers are used directly for those applications in which they act as reactants or electrodes for chemical and serve electrochemical reactions. An important field of application here is the use in plants for the production of aluminum, in which coking products produced according to the invention can be used as anodes or cathodes, in particular as anodes, without any further

Work steps to change their structure or density must be subjected.

If higher mechanical, electrical and, in particular, thermal requirements are placed on the coking products according to the invention, then the above-mentioned optional working steps f) - h) can be carried out after the working steps a) - e) of the method according to the invention. In this way, coking products produced according to the invention can be used as an intermediate product for the production of high-quality graphite elements, as are required, for example, as electrodes in the melting or in the metallurgical treatment of steels in an electrical steel plant.

By using a carbon carrier material consisting of predominantly liquid or liquefiable constituents as the starting product, it is possible to produce a coking product with low porosity. The procedure according to the invention ensures that the smallest possible amount of gas bubbles is included in the coking product obtained. The dimensions of the container determining the shape of the coking product according to the invention can be selected so that, taking into account any machining allowance that may be required, they correspond to the final dimension adapted for the respective application.

The container provided according to the invention can be made in a manner known per se from a sufficiently temperature-resistant steel sheet. In order to facilitate the removal of the finished coking product from the container in work step e), the container can be covered at least in sections with a sliding layer on its inner surfaces surrounding the interior of the container. For this purpose, a separately prefabricated liner, tightly fitting against the inner surface of the container, can be introduced into the interior of the container or a coating consisting of a suitable material can be applied directly to the relevant inner surface. A light metal material, in particular an aluminum material, but also a thin steel sheet can be used as the material for the sliding surface.

In step b) of the method according to the invention, the flowable carbon carrier material is introduced into the container via the filler opening

Introduced interior of the container. The filling opening can be formed by a filling tube or the like that by a cover, a wall or a lid of the container in the bounded by it

Interior is guided.

In order to increase the flowability of the liquid or meltable carbon component added to the container according to the invention, it may be expedient to preheat the carbon component itself or the entire carbon carrier material before filling it into the interior of the container. The preheating is preferably carried out in such a way that the meltable carbon component which may be present and which is to be attributed to the liquid component is already liquefied when it reaches the container. However, the heating in the container can also take place in such a way that the carbon carrier material is first optimally liquid and then the coking process begins.

According to a first variant, the filling can take place in such a way that the total amount of carbon carrier material to be coked is first filled into the container (work step b)) and the heating only after filling to the coking temperature and holding at the coking temperature is carried out (step c)), that is, the heating of the

Carbon material only begins after filling the

Carbon carrier material (step b)) is completed.

According to a second variant, it is also possible, with the heating of a partial volume filled in the container, for the generation of the

Coking product required total amount of carbon carrier material (step c)) to start while another

Carbon carrier material is still filled into the interior (work step b)) -

While the first variant enables simplified process control, the second variant enables the production of particularly dense, high-quality coking products with minimal porosity.

The coking temperatures set according to the invention during the coking process (step c)) are typically 450-900 ° C., with coking temperatures of at least 600 ° C. within a practical coking period even for large volumes

Coking products a complete coking in the technical sense can be achieved safely.

At the same time, by setting the coking temperature in the range of 450 - 900 ° C, it is ensured that sufficient flowable carbon carrier material is always available in the process to automatically fill the pores created in the coking by the degassing processes in the partial volume of carbon carrier material . The penetrating flowable carbon carrier material, which fills the openings and cavities left behind by the gas inevitably formed during coking according to the invention ensures an optimally high density of the coking product obtained.

It has been shown that in the method according to the invention, the electrical conductivity of the products produced according to the invention can be influenced directly by adjusting the coking temperature. The electrical conductivity increases with increasing coking temperature. By setting high coking temperatures, electrical conductivities can therefore already be achieved on the coking product produced according to the invention, which allow a direct graphitization or another direct use of these products after the coking process according to the invention. For example, products produced according to the invention can be used directly as anodes or cathodes, in particular as anodes, in the production of aluminum.

At a coking temperature of at least 650 ° C, in particular at least 700 ° C, there is a further significant reduction in the electrical resistance, resulting in optimally low resistances of 10-50 ohms and a concomitant optimal electrical conductivity

Coking temperatures of at least 800 ° C result. With a suitable setting of the coking temperature of usually at least 800 ° C., a longitudinal graphitability of the coking product can already be achieved in the course of the process according to the invention.

At a temperature above an upper limit of 1200 ° C

Coking temperature no longer improves the conductivity, so that the range of coking temperature can in practice be limited to at most this upper limit.

In order to ensure that as few gas bubbles as possible are caught in the coke, the invention sees a suitable temperature and quantity regime, especially when going through the temperature range of 450 - 600 ° C, to a) ensure that a sufficient amount of liquid

Carbon carrier material is present in order to ensure automatic replenishment of the pores formed, b) at the same time keeping the amount of liquid carbon carrier material as low as possible in order to promote outgassing and removal of the gas bubbles which form, c) allowing the coking process to proceed quickly and d ) a spontaneous coking and associated "freezing" of

Avoid gas bubbles.

The coking time over which the carbon carrier material is kept at the respective coking temperature is directly dependent on the volume heated in each case. In any case, the coking time is to be dimensioned such that the carbon carrier material held at the coking temperature is completely coked in the technical sense after the coking time has ended. The coking time depends on the volume to be coked and, in the case of successive filling, on the progress of the filling process. Typical coking times for larger-volume coking products, such as electrodes, are in practice from 6 h to 96 h. When generating

Coking products with a smaller volume or small cross-sections can also last less than an hour.

In order to escape the gas produced during coking from the

Carbon support material can support the inside of the container existing atmosphere can be extracted. This creates a vacuum in the interior of the container above the carbon carrier material filled into it, which can reach as far as a vacuum. A suitable one for this

Absolute pressure is in the range of 1 to 50 hPa.

The manner of filling the mold (step b)) and heating (step c)) can be selected in the method according to the invention depending on the requirements placed on the density distribution of the

Coking product produced according to the invention. If, for example, there is a requirement that a maximum density over a sufficient thickness should be present in the outer edge areas of the coking products, whereas a certain residual porosity is accepted in the central core area, it may be sufficient if a stationary container has the total volume filled in the container is arranged on flowable heating element detecting carbon carrier material. In this case, the coking process proceeds in the direction of the core region of the carbon carrier material starting from the edge region of the carbon carrier material adjoining the inner surface of the container, which is first and most intensely affected by the heat generated by the heating device. The gas bubbles formed during coking can escape through the core area of the carbon carrier material, which is still liquid over a long period of time. At the same time, liquid carbon carrier material is forced out of the liquid core area into the pores left by the gas bubbles in the edge area that has already been coked, so that an optimally dense edge area of considerable thickness is obtained in the finished coking product. Only in the last stage of coking, namely when the central core area is also coked, can gas bubbles be trapped there. However, the diameter of the core area affected by the resulting porosity is in comparison to the thickness of the optimally dense surface layer of the one produced according to the invention Coking product so small that it is negligible in applications such as electrodes for reduction furnaces.

A porosity which is minimized over the entire cross section of the coking product produced according to the invention and the associated optimized density can be achieved in that during step c) a relative movement takes place along the longitudinal axis of the mold between the respectively heated carbon carrier material and the heating zone generated by the heating device. This relative movement can take place continuously or step by step. In the case of a continuous relative movement, the speed of this movement can also be varied depending on the progress of the carbonization of the carbon carrier material. Likewise, in the case of a gradual relative movement, in which the heating zone or the container remains in one position for a certain length of time until the heating zone or the container moves to the next position, the

The duration of action of the heat on the volume of carbon carrier material detected by the heating zone can be controlled by adjusting the dwell time.

By placing the heating zone relative to the carbon support material or that

Carbon carrier material is moved relative to the heating zone, it can be achieved that the coking process not only as in the above-explained variant of the method according to the invention from the outer edge to the central core area of each of the heat of the heating device

Volume of the filled in the interior of the container

Carbon carrier material progresses, but at the same time also in the direction of the relative movement. In this way, a uniform increase in the respective coked volume of the carbon carrier material can be achieved over the entire cross-section, and this can be used to ensure that a high density is also present in the core area of the coking product obtained according to the invention. According to a first variant of this embodiment of the method according to the invention, the heat given off by the heating device in the heating zone in each case only covers a partial volume of the carbon carrier material filled into the interior that extends over a specific partial section of the height of the interior of the container, the carbon carrier material filled into the interior during the heating (step c)) stops, whereas the heating zone generated by the respective heating device is moved against the direction of gravity towards the upper end of the container, starting from the bottom arranged in the direction of gravity. The part of the volume contained in the interior of the container that is heated from the heating device to coking temperature

Carbon carrier escaping gas bubbles can with this

Design through the liquid carbon carrier material, which emerges above the partial volume of the carbon carrier material that is in the coking process (work step c)) and is captured by the heat of the heating device, escape upward against the direction of gravity, while at the same time due to the force of gravity, liquid carbon carrier material with gravitational pressure into the im already coked

Carbon carrier material urges openings and cavities left behind by the gas bubbles and fills them, so that an overall dense, largely pore-free coking product is automatically obtained.

It proves to be particularly advantageous here that, in the method according to the invention, the filling of the container and the heating of the volume of carbon carrier material contained in the container can take place at the same time. This way the amount of flowable

Control the carbon carrier material that is above this partial volume during the coking of the partial volume captured by the heat of the heating device in such a way that on the one hand the distance covered by the gas bubbles through the still liquid carbon carrier material is optimally short, but on the other hand that on the already coked carbon carrier material load-bearing column of flowable carbon support material is so large that there is always a sufficient amount of flowable carbon support material above the already coked carbon support material partial volume and optimally the displacement of the flowable carbon support material into the pores of the already coked carbon support material by the

Dead weight of the still liquid carbon carrier material is supported.

In the case of a stationary mounted container, a relative movement between the heating zone and the carbon carrier material contained in the container can be brought about by moving the heating device generating the heating zone along the container.

Alternatively, however, it is also possible to have a stationary, over the entire length of the volume filled in the container

Provide carbon support material heating device which is divided into several heating segments in the longitudinal direction of the container. These can then be activated and deactivated successively, so that a continuous or step-wise movement of the heating zone generated by the heating segments of the heating device along the container is achieved.

In another variant of the method according to the invention, the heat given off by the heating device in the heating zone likewise only captures a partial volume of the volume filled into the interior that extends over a specific section of the height of the interior of the container

Carbon carrier material, but here the heating device is arranged in a stationary manner, while the carbon carrier material filled in the container is moved relative to the heating zone generated by the heating device.

Basically, the container can be filled with it

Carbon carrier material are moved along the fixed heater. In a particularly productive embodiment of this method variant based on a fixed heating device, which is also optimal

procured coking products results, however, the container is mounted in a fixed position, wherein a drain opening is provided in the bottom of the container, through which the coking product as from the respectively solidified

Carbon carrier material formed strand is continuously removed from the container (work step e)). In this embodiment, the container is designed in the manner of a casting mold. At the same time it is

Heating device mounted on the container and the withdrawal speed with which the coked coke product is continuously removed as a strand from the container, selected so that the carbon carrier material filled in the flowable state on its way to the

Discharge opening in the technical sense is completely coked and solidified accordingly. In addition to the increased productivity, there is also the particular advantage that the volume of flowable carbon carrier material, which is above the already coked part of the carbon carrier material in the container, can be set in such a way that, on the one hand, the path from which in the coking process (work step c)) located partial volume of escaping gas bubbles has to be covered, is short and on the other hand there is always sufficient liquid carbon carrier material available to fill the pores left by the gas bubbles in the already coked carbon carrier material. The coking product drawn off as a strand from the container can optionally be accelerated to allow rapid further processing. From the coke product strand obtained, coke products of the respective

desired length can be divided.

In the design variants in which there is a relative movement between the carbon support material and the heating source, the

The speed of the relative movement depends on the diameter or cross section of the product to be produced. The speed increases increasing diameter or cross-sectional size due to the proportion of carbon carrier material used to coke the respective heating zone. When producing cylindrical electrodes with typical diameters in practice, the speed of the relative movement lies between the heating zone and that contained in the container

Carbon carrier material typically in the range of 0.025-1.5 m / h, in particular 0.05-0.5 m / h.

The degassing (step d)) of the gas escaping from the carbon support material in the coking process (step c)) can be supported in that the carbon support material contained in the container is at least temporarily set in motion.

For this purpose, for example, a vibration device or the like can be provided which excites the carbon carrier material contained in the container as a whole or in regions to vibrations, which ideally lie in the range from 0.5 Hz to 50 kHz.

According to the invention for heating the carbon carrier material

The heating device used can be designed in such a way that it brings about a specific temperature profile within the carbon carrier material contained in the container and captured by the heat of the heating device. For example, in the case of the process variants in which there is a relative movement between the heating zone generated by the respective heating device and the carbon carrier material, it may be expedient, for example, to operate the heating device in such a way that the partial volume of carbon carrier material entering the effective area of the heating device slowly increases the respective coking temperature is brought up, that is to say that the heating power which acts on the respective partial volume of carbon carrier material increases the further the respective partial volume enters the effective area of the heating device and the longer it is exposed to the heat given off by the heating device. The method according to the invention provides coking products which already have a geometry close to the final dimensions during coking. This eliminates the conventional steps in the manufacture of electrodes

Coke preparation, mixing, shaping and first firing and the possibility opens up to impregnation and a second firing of the

coking product produced according to the invention for the production of a fully graphitized end product. That's how it delivers

method according to the invention already without impregnation

Coking product of high strength and density. These are characterized by the fact that they have an average density of at least 1.4 g / cm ³ , densities of at least 1.5 g / cm ^{3 being} regularly achieved.

The fact that in the inventive method already in

Coking process is a monolithic structure close to the final dimensions, this is characterized by a high mechanical strength.

Furthermore, the spatial expression of the physicochemical coke properties can be controlled through the targeted application of heat.

In particular, a high electrical conductivity can be achieved in this way

Set the longitudinal direction and a low coefficient of thermal expansion.

The invention is explained in more detail below on the basis of a drawing illustrating an exemplary embodiment. Each shows schematically:

Figures 1a - 1d a first device for producing a

Coking product at four operating times spaced at equal intervals, each in a section along the longitudinal axis of the device; Figures 2a - 2d a second device for producing a

Coking product at four operating times spaced at equal intervals, each in a section along the longitudinal axis of the device;

Fig. 3 shows a third device for producing a

Coking product in a section along the longitudinal axis of the device;

Fig. 4a shows a fourth device for producing a

Coking product in a section along the longitudinal axis of the device;

Fig. 4b a generated in the device shown in Fig. 4a

Coking product in a longitudinal section.

The device 1 for producing a coking product VK shown in FIGS. 1a-1d comprises a container 2, which is vertically aligned with its longitudinal axis L and is shaped like a cylinder tube and is made of a heat-resistant material, such as a steel customary for this purpose. The container 2 delimits an interior space 3 which widens in a funnel shape in an upper section 4 in the direction of the upper edge of the container 2.

The slim, cylindrical shape of the interior 3 is selected such that the coking product VK produced in the device 1 has an equally slim cylindrical shape at the end of the coking process carried out in the device 1, which is optimally approximated to the shape that the coking product VK or should have a graphite product produced from it. The dimensions of the coking product VK can be used

Include machining allowance, which is required for a final processing to the coking product VK or a product thereof Graphite product its prescribed dimensional accuracy or

To give surface texture. Thus, the shape and dimensions of the cylindrical shape shown by the interior 3 of the container 2 correspond to the shape that graphite electrodes must have in order to be able to be used in arc furnaces in steelworks. In the same way, the shape of the interior allows 3 other shapes of

Coking products, such as coking

Blocks formed of carbon support materials or the like can be imaged. Their shape can then, for example, be optimally adapted to the conditions in plants for producing aluminum, if necessary also including the required machining allowance.

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

The opening at the top of the container 2 is closed by a removable cover 6.

Through the cover 6 is a filling tube 7 for filling the interior 3 of the

Container 2 performed with a flowable carbon carrier material K.

In addition, a suction pipe 8 is passed through the lid 6, which is connected to an evacuation device, not shown here, via which in the

Interior 3 a suppressor for suction of gases present in the interior 3 can be generated.

With its underside, the container 2 stands on a base element 9 which closes the container 2 on its underside. The device 1 further comprises an electrically operated, controllable heating device 10, which is placed with its heating coils 11 in a ring shape and with play around the outer surface 12 of the container 2. The height H10 of the

Heating device 10 corresponds to a small fraction of the height H3 of

Interior 3 of the container 2. For example, the height H3 can be up to 15 m, whereas the height H10 is typically only 1 m.

The heating device 10 is carried by an actuating device 13, which is set up in a manner known per se to move the heating device 10 in the vertical direction V along the container 2. For this purpose, the adjusting 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 also comprises a device 16 which is provided to apply vibrations in the range from 0.5 Hz to 50 kHz to the liquid carbon carrier material K filled in the interior 3 of the container 2. In order to achieve the most intensive possible effect on the still liquid, uncoked volume of the carbon carrier material K, the vibrating device 16 can also be carried by the actuating device 13 and moved along the container 2 during the coking process with the heating device 10. The vibration device 16 is seated here

preferably above the heating device 10, in order to achieve the best possible effect of the movement of the fluid that is still triggered by it

Carbon carrier material K to effect.

To produce a columnar coking product VK

Interior 3 of the container 2 via the fill pipe 7 with flowable

Filled carbon carrier material K until the mirror SK of the carbon carrier material K contained in the interior 3 is located approximately in the region of the transition between the funnel-shaped upper section 4 and the cylindrical part of the interior 3 lying underneath. The heating device 10 is positioned during the filling process in an initial position at the lower end of the container near the bottom element 9.

After the container 2 is filled with the flowable carbon carrier material K, the heating device 10 is charged with, for example, electrical energy, so that the partial volume of the carbon carrier material K lying in the effective range of the heating zone generated by the heating device 10 gradually increases to a coking temperature of 450-900 ° C , in particular 650 - 850 ° C, is heated. As a result of the heating, decomposition processes begin in the partial volume that is heated in this way, as a result of which it is still fluid

Carbon carrier material K gases are released in the form of

Gas bubbles G against the direction of action SR of gravity in the

Ascend carbon carrier material K. The space freed up by the decomposition processes in the carbon carrier material K is

Gravity effect automatically pushing flowable

Carbon carrier material K of the carbon carrier material column present in the interior 3 of the container 2 is replaced. This process continues until the partial volume heated in each case by the heating device 10 in the heating zone it produces has coked completely in the technical sense and has assumed a solid form. Since all that have been released by gas formation

Cavities in each case directly by pressing flowable

Carbon carrier material K have been filled, the density of the part of the carbon carrier material K so coked is at least 1.4 g / cm ³ .

The detachment of the gas bubbles G from the carbon carrier material K is supported mechanically on the one hand by the vibrations that occur via the

Device 16 can be induced in the carbon carrier material K. On the other hand, the removal of the gas bubbles G from the carbon carrier material K is promoted in that a vacuum is maintained via the suction pipe 8 in the interior 3 of the container 2, which can reach a vacuum. Since the coking by symmetrical heating from the sides of the

Coking runs from the outside inwards. When the outer layer is coked, liquid is initially viscous, both in the core area and in the layer above it

Carbon carrier material K is present, through which the gas bubbles G can escape and possible pores are closed. This enables a high density of the coking product obtained. When the core area is coked, carbon carrier material K can flow in from the layer above it. Here, too, the pores are closed.

Should smaller gas bubbles in the core area KB of the

Coking product VK be trapped, so this has little

Effect on the mechanical properties, since the neutral axis of the columnar coking products VK runs along the relevant core area and this area is therefore not exposed to increased tensile or compressive stresses in use.

After the partial volume of the

Carbon carrier material K is coked, the heating device 10, which is still held in the heating mode, and with it the likewise still active one

Vibration device 16 by means of the actuator 13 against the

Direction of action SR of gravity shifted 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 the vibrating device 16 coupled to it is dimensioned such that the partial volume of the carbon carrier material K located in the effective range of the heating zone generated by the heating device 10 gradually heats up and then over a coking period on the respective one

Coking temperature is kept for one in a technical sense complete coking and associated complete solidification is sufficient. In practice, conveyor speeds for this are

Heating device 10 typically in the range of 0.025-1.5 m / h,

in particular 0.05 - 0.5 m / h.

The movement of the heating device 10 continues until the upper section of the carbon carrier material K adjacent to the mirror SK of the carbon carrier material K is also coked. The mirror SK of the

Carbon carrier material K is due to the from

Carbon carrier material K escaped gas and thus

accompanying volume loss compared to the state when the interior 3 of the container 2 is refilled.

After the upper area BP of the carbon carrier material K adjoining the mirror SK is coked and has assumed a solid shape, the container 2 is opened and the one formed in its interior 3

Coking product VK taken from the interior 3. The on the

Interior 3 bounding inner surfaces of the container 2 existing liner or sliding layer 5 facilitates the removal of the coking product VK.

It turns out that in the upper area BP of the coking product VK the required density of at least 1.4 g / cm ^{3 has} not been reached because there is no longer sufficient flowability there during the coking

Carbon carrier material K was available to fill the voids left by the gas bubbles G being formed, the area BP in question is separated. It can be reused by grinding it into fine particles, which are solid

Carbon components can be added to the carbon carrier material K, which are used for the production of further coking products VK in the

Device 1 can be provided. The coking product VK thus obtained is used to produce a

Graphite electrode, as is required in an electrical steel plant, is subjected to a customary graphitization process in order to give it a graphitic structure. Because of the device 1 in the above

described manner already obtained after the first coking

monolithic, near-net-shape geometry, are the case with

conventional processes, grinding, mixing and shaping processes are just as obsolete as the associated first firing. Depending on the density of the product, the impregnation step can also be omitted. If it turns out that the density of the coking product VK obtained is not sufficient, before further processing of the coking product VK into the graphite product, i.e. to the graphite electrode, an impregnation to increase the density can also be carried out in a conventional manner.

The structure of the device 101 shown in FIGS. 2a-2d for producing a coking product VK corresponds to that of the device 1 shown in FIGS. 1a-1d, with the difference that in the device 101 instead of the fixedly mounted filling pipe 7 provided in the device 1 a filling tube 107 which can be inserted and pulled out in the manner of a lance into the interior 3 of the container 2 of the device 101 is provided. The maximum insertion length of the filling pipe 107 is dimensioned such that the filling pipe 107, when fully inserted into the interior 3, ends just above the height H10 over which the heating zone generated by the heating device 10 extends in the starting position of the heating device 10 (FIG. 2a). This avoids the negative effects of splashes that can be triggered during the coking process.

In order to produce a column-like coking product VK, the interior 3 of the container 2 is filled with a partial volume of flowable carbon carrier material K in the device 101 via the filling pipe 107 until the mirror SK of the carbon carrier material K contained in the interior 3 ends above the height H10 over which the heating zone generated by the heating device 10 in its starting position extends (FIG. 2a).

Then this becomes the lower section of the one to be manufactured

Partial volume of the carbon carrier material K forming the coking product VK in the stepwise and controlled manner for the device 1

Coking temperature brought.

With the onset of coking, filling tube 107, raised by a corresponding amount of height, becomes quasi-continuous

flowable, if necessary preheated to liquefy

Carbon carrier material K supplied and the heating device 10 with the vibrating device 16 coupled to it is moved along the container 2 by means of the actuating device 13 in the manner already described for the device 1. The movement of the via an actuator, not shown here

Height-adjustable filling pipe 107 and the heating device 10 are coordinated with one another 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 carbon carrier material K remains constant. The free end of the

Filling tube 107 always near the level SK of the filled in the container

Carbon carrier material K until the maximum fill level in container 2 is reached.

The height of the mirror SK of the carbon carrier material K is kept such that above the partial volume of the carbon carrier material K in the coking there is always a sufficient amount of flowable carbon carrier material K available to fill the cavities left by the gas bubbles G, the from the to the

Warm coking temperature and exit at the coking temperature held partial volume of the carbon support material K. The path that the gas bubbles G through the liquid carbon carrier material K must be covered is shorter than in device 1, so that an even more optimized density of the coking product VK can be achieved.

FIG. 3 shows a device 201 for producing a coking product VK, in which, in contrast to the devices 1 and 101, a heating device 210 provided on the device 201 is mounted in a stationary manner, that is to say it stands still during operation, whereas the one to be coked

Carbon carrier material K moves along the heater 210 and in this way along the heater 210 to a solid

Coking product VK is coked in the manner of a continuous

Continuous casting process is continuously withdrawn from the device 201.

For this purpose, the device 201 has a container 202 which delimits an interior space 3 which, like the interior spaces 3 of the devices 1, 101, widens in a funnel shape in an upper region and by a cover 206

is completed. A suction pipe 208 and a filling pipe 207 arranged in the manner of the filling pipe 7 of the device 1 are passed through the cover 206 here, as in the case of the covers 6 of the devices 1, 101.

The cylindrical region 217 of the interior 203 arranged under the funnel-shaped upper region is designed to be open at the bottom in the manner of a mold and is considerably shorter than in the devices 1, 101. The section of the container 202 surrounding the region 217 is seated in the ring-shaped heating device 210, which extends over a substantial part of the height of the area 217. The heating coil 211 are the

Heating device 210 can be regulated in segments in order to achieve an optimal temperature profile in the effective range of that generated by heating device 10

To allow heating zone located partial volume of the carbon support material K.

To produce a coking product VK, the lower outlet opening of the mold-like region 217 of the interior 203 is first covered with a Plug closed and filled a first partial volume of carbon carrier material K into the interior 203 of the container 202 via the fill tube 207.

By means of the stationary heating device 210, the carbon carrier material K located in the effective area of the heating zone generated by the heating device 210 is controlled step by step, heated to the coking temperature and held there until it is completely coked in the technical sense and has assumed a solid form.

In the course of the coking process, this becomes coked

Carbon carrier material K as a strand is pulled continuously from the mold-like region 217 of the interior 203 of the container 202 by means of the stopper via its lower opening. At the same time, new, possibly preheated, carbon carrier material K is also continuously filled into the container 202 via the filling pipe 207. The lower opening region 218 of the region 217 can widen in a funnel shape in the direction of gravity SR in order to

To facilitate pulling out the stranded coking product VK. The pull-out forces are dimensioned such that the coking product is continuously withdrawn from the container 202 despite the underpressure A / akuums present in the container 202 above the carbon carrier material filled into it.

The process of pulling off and refilling takes place synchronously with one another so slowly that the length of time over which the

Heating device 210 passing carbon carrier material K at the

Coking temperature is maintained which corresponds to the coking time required for its complete coking in the technical sense.

As with the device 101, the height of the level SK of the flowable carbon carrier material K is above that already as a result of the

Coking hardened carbon carrier material K adjusted so that on the one hand the gas bubbles G that are in the coking Carbon carrier material K emerge, only have to travel a short way through the flowable carbon carrier material K until they are sucked out via the suction pipe 208 after exiting the carbon carrier material K, but on the other hand there is always a sufficient amount of liquid carbon carrier material K available to pass through into the solidifying carbon carrier material K pressing liquid

Carbon carrier material K to fill the pores left by the gas bubbles G. Even with a device of the type shown in FIG. 3, optimally dense coking products with optimally homogeneous can thus be obtained

Generate property distribution.

The outgassing of the gas bubbles G can be supported by a vibration device 216, which, as in the case of the devices 1, 101, is above the

Heating device 210 is arranged, but here, according to the fixed arrangement of the heating device 210, is stationary. As already mentioned, a vacuum / vacuum can also be applied to the container 202, which functions in the manner of a mold, in the region above the carbon carrier material K filled into it, in order to outgass the gas

To support coking process-forming gases G from the carbon carrier material K in the container 202.

That continuously withdrawn as a strand from the device 201

Coking product VK passes through a cooling section 219 after it emerges from the container 202, in which it is accelerated to room temperature. The strand is then cut off in a cutting device 220

Coking products VK with the desired length divided in a manner known per se.

As in the continuous casting of metal melts, two or more such mold-like container regions 217, each with a heating device 210 arranged thereon, can be connected to a central distributor (not shown here) which feeds the mold-like container regions 217 with carbon carrier material K. and a vibrator 216 also mounted thereon for maximum productivity.

FIG. 4a shows a device 301 for producing a coking product VK, which comprises a pot-shaped container 302 made of a suitable steel material, which is closed by a lid 306. A suction pipe 308 is guided through the cover 306 and is used to evacuate the interior 303 surrounded by the container 302 to one not shown here

Suction device is connected. The container 302 sits in one

Heating device 310, the stationary, annular heating spiral 311 of which extends over the entire height of the container 302, so that the heating device 310 can generate a heating zone correspondingly extending over the entire height of the container 302.

To produce a block-shaped coking product VK (FIG. 4b), the lid 306 is removed from the container 302 and becomes flowable

Carbon carrier material K filled in the interior 303 of the container 302. The container 302 is then closed by putting the lid 306 on and the carbon carrier material K contained in the container 302 is brought to a coking temperature of 450-900 ° C. When the coking temperature is reached, the coking and solidification of the carbon carrier material K begins from the lateral inner surfaces of the interior 303. The core region KB of the carbon carrier material K remains highly fluid over a long period of time, so that gas bubbles G reaching there, like those resulting from the Coking partial volumes of the

Carbon carrier material K emerging gas bubbles G, move for a long time against gravity in the direction of the mirror SK of the carbon carrier material K contained in the container.

If the coking process has progressed so far that the core area KB also cokes, it can happen that smaller gas bubbles G are trapped in the inner core area KB. As a result of this there Porosity is harmless, however, since coking products of the type produced in the device 301 are usually used for applications in which, in particular, in the region of the outer edge sections of the

The coking product VK places the highest demands on conductivity and stability, while the quality of the core area KB only plays a subordinate role. Such requirement profiles arise, for example, in plants for the production of aluminum, if there

Coking products VK of the type produced according to the invention are to be used as anodes or cathodes, in particular as anodes.

The flowable carbon carrier material K used in the devices 1, 101, 201, 301 for producing the respective coking product VK consists in each case of the distillation of petroleum products and the

Recovery of coal-based products, such as tars and their derivatives, pitch, flowable bitumen, resins and products from the processing of biomass, such as cellulose products, sugar and starch or other products that can be coked. This carbon carrier material K is optionally with granular coke or graphite with a grain size of at most 10 mm and optionally one or more additives, such as iron oxide to reduce the puffing effect, a boron source, such as boron carbide, to reduce the coefficient of thermal expansion or to improve the generated Crystal structure, or carbon or graphite fibers, which improve the mechanical properties and also reduce the coefficient of thermal expansion, mixed. The carbon carrier material K used in each case is liquid at the process temperature in such a way that it flows under the action of gravity into the interior 3, 103, 203, 303 bounded by the container 2, 102, 202, 302. REFERENCES

Figures 1, 2

1 device

2 device 1 containers

3 interior of the container 2

4 upper section of the interior 3

5 sliding layer

6 Lid of the container 2

7 filling pipe (filling opening)

8 suction pipe

9 floor element

10 heating device

11 heating coil of the heating device 10

12 outer surface of the container 2

13 adjusting device

14 Linear guide of the actuating device 13

15 linear actuator actuator 13

16 vibration device

101 Device for producing a coking product

107 filling pipe

BP region of the carbon carrier material K H10 adjacent to the mirror SK Height of the heating device 10

H3 interior height 3

Figure 3

201 Device for producing a coking product

202 containers designed in the manner of a mold

203 interior of the container 202 designed in the manner of a mold

206 lid

207 filling pipe (filling opening)

208 suction pipe

210 heating device

211 heating coil of the heating device 210

216 vibration device

217 lower cylindrical region of the interior 203 of the container 202 which is open at the bottom

218 lower funnel-shaped opening area of area 217

219 cooling section

220 cutting device Figures 4a, 4b

301 Device for producing a coking product VK

302 containers

303 interior of container 302

306 lid

308 suction pipe

310 heating device

311 heating coil of the heating device 310

KB core area of the carbon carrier material K

General G gas bubbles

K flowable 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 the interior 3 of the container 2, 202, 302

V vertical direction

VK coking product

Claims

PATENT CLAIMS

1. A process for producing a coking product (VK), comprising the following steps:

a) Providing a container (2,202,302), the

- An interior (3) bounded

and

- A fill opening for filling a flowable

Carbon carrier material (K) in the interior (3)

such as

- A heater (10,210,310) for heating the in the

Interior (3) of the container (2,202,302) filled

Carbon carrier material (K)

includes;

b) introducing the flowable or pourable carbon carrier material (K) via the filling opening into the interior (3) of the container (2,202,302), the carbon carrier material (K) at least one liquid or meltable, coking agent

Carbon component and optionally at least one solid carbonizable carbon component and also optionally includes at least one additive, which serves to adjust the properties of the carbon carrier material (K); c) heating the carbon carrier material (K) filled into the interior (3) of the container (2,202,302) to a coking temperature by means of the heating device (10,210,310), the carbon carrier material (K) heated to the respective coking temperature being kept at the coking temperature for as long as until that held at the coking temperature

Carbon carrier material (K) by coking to the

Coking product (VK) is solidified and

d) being gas, which during heating and holding

(Work step c)) escapes from the carbon carrier material (K), from which the container (2,202,302) is derived;

e) removing the coking product (VK) from the container

(2,202,302).

2. The method according to claim 1, characterized in that the liquid or meltable carbon component of the carbon carrier material (K) consists of at least one component from the following group: "Residues from the distillation of petroleum, products obtained from the recycling of coal, tars and their derivatives "Pitch, flowable bitumen, resins and products from the processing of biomass, cellulose products, sugar and starch".

3. The method according to any one of the preceding claims, characterized in that the carbon carrier material (K) contains a solid carbon component consisting of at least one

Component of the following group consists: “in granular form

existing coke, coal, bitumen in solid form, lignites,

Anthracite coal, graphite, products from the recycling of

Carbon fibers ”.

4. The method according to any one of the preceding claims, characterized in that the carbon carrier material (K) contains an additive from the following group: "iron oxide, titanium oxide, boron and boron compounds".

5. The method according to any one of the preceding claims, characterized in that the heating of the

Carbon carrier material (K) (step c)) only begins after the filling of the carbon carrier material (K) (step b)) has been completed.

6. The method according to any one of claims 1 -4, characterized

characterized that the warming of the

Carbon carrier material (K) (step c)) begins while the carbon carrier material (K) (step b)) is filled into the interior (3).

7. The method according to any one of the preceding claims, characterized in that the coking temperature in

Step c) is 450 - 900 ° C.

8. The method according to any one of the preceding claims, characterized in that the coking time in step c) is up to 96 h.

9. The method according to any one of the preceding claims, characterized in that the atmosphere present in the interior (3) of the container (2,202,302) is sucked off in order to remove from the escaping gas escaping to the carbonization temperature heated carbon carrier material (K) from the container (2,202,302) forced (step d)).

10. The method according to any one of the preceding claims, characterized in that during step c) one aligned along the longitudinal axis of the container (2,202,302)

Relative movement between the respectively warmed

Carbon carrier material (K) and the heating device (10,210,310) takes place.

11. The method according to claim 10, characterized in

that the heat given off by the heating device (10, 210, 310) only covers a partial volume of the carbon carrier material (K) filled in the interior (3) that extends over a certain section of the height of the interior (3) of the container (2), Interior (3) filled carbon carrier material (K) stands still during work step c) and that the heating zone

(10,210,310) is moved from the bottom arranged in the direction of gravity against the direction of gravity in the direction of the upper end of the container (2,202,302).

12. The method according to claim 10, characterized in that the heat given off by the heating device (10, 210, 310) only in each case extends over a certain partial section of the height of the interior (3) of the container (2, 202, 302) of the partial volume of the interior (3) Carbon carrier material (K) detects that the heating device (10,210,310) is arranged in a fixed position and that the filled in the container (2,202,302) Carbon carrier material (K) is moved relative to the heating device (10,210,310).

13. The method according to claim 12, characterized in that a discharge opening is provided in the bottom of the container (2,202,302), through which the coking product (VK) as the strand formed from the respectively solidified carbon carrier material (K) is continuously removed from the container (2,202,302)

(Step e)).

14. The method according to any one of the preceding claims, characterized in that the carbon carrier material (K) within the container (2,202,302) is at least temporarily set in motion.

15. The method according to any one of the preceding claims, characterized in that the density of the coking product (VK) removed from the container (2,202,302) at least

1.4 g / cm ³ .