WO2013143653A1 - Process and apparatus for producing metallurgical coke from petroleum coke obtained in mineral oil refineries by coking in "non-recovery" or "heat-recovery" coking ovens - Google Patents

Description

 Process and apparatus for producing metallurgical coke from petroleum coals produced in petroleum refineries by coking in non-recovery or heat-recovery coke ovens

The invention relates to a process for the production of metallurgical coke from petroleum coals produced in petroleum refineries by coking in "non-recovery" or "heat-recovery" coke ovens, which emanates from oil refining produced or produced petroleum coals, which from the outset a Volatile content of 15 to 19 weight percent and has an ash content of up to 2 percent by weight, and which is compressed in a coke oven type "non-recovery" or "heat recovery" for cyclic coking is given, which is equipped with at least one externally heated burner so that the primary heating space or the secondary heating space below the coke oven chamber or both are heated to a temperature between 1000 ° C to 1550 ° C, and within a period of less than 120 hours the volatiles contained in the petroleum coals completely outgassing, with a metallurgical Coke with a CSR strength of at least 44% and a CRI reactivity ät less than 33%, which is suitable for use as metallurgical coke. The invention also relates to a coke oven, which is constructed according to the construction principle of the "non-recovery" or "heat-recovery" coke ovens, which contains a primary heating space, which is equipped with burners which heat the primary heating space.

In the processing of mineral oil and petroleum in refineries to petroleum products in addition to the desired products also a so-called petroleum coke is formed, which is formed in distillation processes, reforming, hydrogenation, and purification operations of a petroleum refinery from high-boiling residues. This typically consists of over 88 weight percent carbon, and a volatile content (VOC) of 8 to 12 weight percent. This petroleum coke is of little commercial interest because it has undesirable properties in many recovery processes, such as low CSR strength and high CRI reactivity, and for that reason finds no suitable markets.

Petroleum coke is often used in niche applications such as metallurgy for electrode production. A use of petroleum coke in metallurgical technology, so for example as a reducing agent in a blast furnace process for the production of pig iron, is not possible because the strength of the petroleum coke is not sufficient for use in blast furnace. In addition, it is known to

CONFIRMATION COPY However, the proportion of admixed petroleum coke due to the low quality of blast furnace coke produced therefrom is limited to orders of magnitude less than 10 weight percent.

Another problem of petroleum coke are impurities that come from the processing of petroleum, and which have been enriched in the discharge of petroleum coke in this. Frequently encountered impurities of petroleum coke are, for example, vanadium, nickel, sulfur, silicon, iron or titanium. Thus, the vanadium content in petroleum coke fractions may be up to 0.17% by weight, the nickel content up to 0.04% by weight and the sulfur content up to 5% by weight. These impurities entail that the petroleum coke can not be readily used for heating purposes, since this would pollute the environment. Another peculiarity of the petroleum coke is to have a lower flame temperature than blast furnace coke or coal. This is undesirable in terms of fuel usage and handling, so it can not be used for many finishing processes. It is therefore sought ways to provide an economic use of petroleum coke.

[0005] A major obstacle to obtaining metallurgical coke by adapting the coking process to the properties of the petroleum coke is, in addition to the impurities and the lack of strength of the product, in turn, a fluctuating proportion of volatiles. The fluctuating volatiles content means that use in a coke oven is difficult to control due to the volatile computable heating properties caused by the volatiles. In general, the majority of the petcoke produced in refineries is provided with a very low volatile content of less than 19% by weight, so that it is unsuitable for use in the "non-recovery" or "heat-recovery" coke oven sustain the self-sustaining combustion and thus coking process. The coking process would then come to a virtual standstill after several coking cycles, with the sole use of petroleum coke as the feedstock in this coke oven, since the heat generated during coking by incineration of the volatiles and stored in the furnace refractory is insufficient Following batches keep the oven temperature at the required high value above 1000 ° C. Another difficulty in the coking of coal is added that petroleum coke has very high propellant pressures during coking, which is due to the low-boiling volatiles contained therein. These result in a significant increase in volume of the coke cake during coking, so to speak, "swelling." It is therefore not possible to coke petroleum in a conventional coke oven, since the walls of a coke oven chamber would be damaged by the increase in volume of the petroleum coke cake during coking Volume enlargement of the petroleum coke cake, which results from the mentioned properties of the petroleum coke cake, also has the consequence that the coke product produced using petroleum cokes in the coal mixture is very difficult to express from a conventional coke oven chamber.

One way to work up and further use of petroleum coke is WO0010914A1. The teaching provides a process of subjecting petroleum coke petroleum coke obtained from a mineral oil petroleum coke precursor material to a thermal fission process at a sufficiently high temperature and for a sufficiently long period of time at a sufficient pressure to obtain a petroleum coke which has a reduced viscosity and precisely adjustable volatiles content of 13 to 50 weight percent. The method also discloses a way to desalt the petroleum coke so that the metal contaminants contained therein are removed. Finally, the teaching also discloses a possibility to reduce the sulfur impurities of the petroleum coke to a reduced and environmentally acceptable proportion, for example by adding desulfurizing agents in a fluidized bed. The method provides a way to provide petroleum coke fractions with a fairly accurate volatiles content and impurities. Petroleum coke fractions with a volatiles content of 15 to 25 percent by weight are also called "petroleum coals", since these are similar in their properties to those of conventional edible or fatty stone coals.

The availability of petroleum with a precisely determinable amount of volatile components and impurities opens up new opportunities to use the obtained petroleum for the production of metallurgical coke. In petroleum processing, a particularly high proportion of petroleum coals with a volatile content of 15 to 19 percent by weight is produced. This product has not been further processed on an industrial scale because of the problems of low energy content, low economy, hazardous propellant pressure during coking, high contamination, and high burnup losses associated with it Product associated with the conventional coking process can not be solved. Laboratory investigations of the metallurgical coke, which is produced from this special fraction of petroleum coke, attest to this, however, a good quality. Examples of these studies are taught in the article by Stukov et al., Increasing the Strength of Metallurgical Petroleum Coke to the Coking Batch, Coke and Chemistry, 2009, Vol. 52, No. 8, pp. 349-352. Since the technical feasibility in the production of metallurgical coke from petroleum coke is not yet secured, there is a need to obtain an executable process for the production of metallurgical coke by coking of petroleum coke in a coke oven.

It is therefore an object to provide a method available that presents petroleum with a share of 15 to 19 weight percent of volatile components and an increased amount of impurities, uses on an industrial scale for coking and provides a coke, which has increased strength and low reactivity, and which is suitable for use as metallurgical coke.

The present invention solves this problem by a method which presents petroleum charcoal with a known volatile content of 15 to 19 percent by weight and a known ash content of up to 2 percent by weight, and then compressed this petroleum under normal conditions with temperatures in the Combined heating chambers between 1000 ° C to 1550 ° C within a period of 120 hours in a coke oven of the type "non-recovery" or "heat recovery" to metallurgical coke, which with at least one burner for heating the Primärheizraums by the im Operation existing gas space is formed above the petroleum coke cake, or is equipped to heat the Sekundärheizraumes below the coke oven chamber or both.

The determination of the volatiles content and the ash content of the petroleum coke is carried out prior to coking by analysis, it does not matter if the analysis is carried out on the grounds of the coke oven plant or the supplier for the petroleum coke. Important for carrying out the method according to the invention is merely that a petroleum coal is presented with a known content of volatile constituents, wherein a range of at least 15 weight percent and a maximum of 19 weight percent is observed. To compensate for the reduced due to the lower proportion of volatile constituents energy content of the petroleum with the above properties, a heating of Primärheizraumes or Sekundärheizraumes must be performed with an external fuel gas, since only this low-energy petroleum coke fraction in a coking reactor of the type Would like to process "non" or heat recovery "to metallurgical coke. Otherwise, a disproportionately long and uneconomical coking time would result because the low energy content of the feedstock is not sufficient to keep the temperatures consistently at the required value above 1000 ° C and thus the high exhaust and radiation losses associated with the process , to compensate.

By using a coke oven of the type "non-recovery" or "heat recovery" can be an insert mixture, which consists mainly of petroleum and is subject to the above properties, but coke, since such a type of coking oven in the operating condition leaves a gas space above the petrol coal cake, which absorbs the resulting high propellant pressures of petroleum coals. It has been found within the scope of the invention that the coke qualities obtained in this way have strengths of more than 44% CSR and reactivities of less than 33% CRI, which makes them suitable for use as metallurgical coke, for example in metallurgical or blast furnace processes. The above values of a coke have a favorable effect on a blast furnace process when it is used in a blast furnace process.

In particular, a process is claimed for the production of metallurgical coke from petroleum coals produced in the petroleum-processing industry, in which

 Petroleum coke from petrochemical processes is subjected to an analysis of the volatiles content and the ash content so that it can be sorted into batches with a known content of volatiles and ash content, and

A petroleum coal charge having a volatiles content of 15 to 19% by weight and an ash content of less than 2% by weight, based on the water and ash-free petroleum charcoal charge, is sorted out and placed in a coal storage bunker or coal storage vessel, and This petroleum coal fraction from the coal storage bunker or coal storage container is first passed through filling machines into a compacting device for compression and then into a coke oven with the dimensions of the type "non-recovery" or "heat recovery" for cyclical coking,

 and which is characterized in that

 • The coke oven is equipped with at least one externally heated burner for heating the Primärheizraums above the petroleum coke cake or for heating the Sekundärheizraumes below the coke oven chamber or both, through the petroleum coke in the coke oven chamber with a hot fuel gas to a temperature of 1000 ° C to 1550 ° C is heated within a time period of less than 120 h, so that a metallurgical coke with a CSR strength value of at least 44% and a CRI reactivity value of less than 33% is obtained. Coke ovens of the type "non-recovery" or "heat recovery" with primary and Sekundärheizraum are known in the art for coking. This type of construction is described in detail, for example, in the article by Walter Buss et al., "Thyssen Still Otto / PACTI Non-Recovery Coke Making System", Iron and Steel Engineer, Association of Iron and Steel Engineers, Pittsburgh, USA, vol. 76, no .1, January 1999, pages 33-38. A coke oven bank made of coke ovens, which are suitable for the coking of coals with high driving pressures, is exemplified by WO201197198A1. When heated, the petroleum tar cake reaches an estimated temperature of 900 to 1100 ° C.

By heating over the compressed petroleum coke cake, the petroleum coals are heated so that a coke of the desired quality results, wherein the proportion of volatile constituents in the petroleum coke rises in the form of crude coking gas from the batch. Part of the degassed components is initially burned substoichiometric at least temporarily with the addition of air in the Primärheizraum for heat generation. The partially combusted exhaust gas mixture is then removed via the side gas channels of the coke oven chamber, and completely burned by further combustion in the Sekundärheizraum. Due to the volatiles contained in the petroleum coals, the petroleum coals are thus also heated from below, so that the heating of the petroleum coarse cake, if one clasps the side door areas, takes place from all sides and a uniform coking quality is achieved. The quality of the resulting coke can be determined as described to give CSR strength values of at least 44% and a CRI reactivity values of less than 33%. The prerequisite is the use of a petroleum charcoal batch which has a volatiles content of 15 to 19% by weight and an ash content of less than 2% by weight, based on the water and ash-free petroleum coal charge.

It is also possible to use a petroleum charcoal whose content of volatile components is determined more accurately. In one embodiment of the invention, the volatiles content of the petroleum coal is 16 to 18 percent by weight. This makes the process easier to control.

To carry out the invention, the petroleum tar cake can in principle be heated from all sides, so that it reaches the desired temperature. In an advantageous embodiment of the invention, the heating of the coke oven is carried out so that the burner flame is introduced horizontally into the gas space above the petroleum coal charge, the so-called Primärheizraum. For this purpose, sitting in an advantageous embodiment in the wall above the coke oven chamber at least one acted upon by a burner with a hot gas or combustion gas burner tube which opens through an opening in the gas space above the petroleum coal, whereby this space is heated with hot gas. The horizontal arrangement of the combustion tubes above the charge ensures that the inflowing gas flows in above the petroleum coke cake into the Primärheizkammer and thereby the direct contact between the coal surface and the combustion air, and thus the undesirable coal or Koksabbrand is reduced. At the same time, a vertical distance of the inserted burner tube to the upper edge of the charge of more than 100 mm is set so that the upper petroleum coats do not burn.

In the context of the invention, it is for example also possible to heat the petroleum coal by further burners, which are arranged in the Sekundärheizraum below the petroleum coke. In a further embodiment, the sole or simultaneous arrangement of at least one burner is claimed at the lateral end openings of the Sekundärheizraumes, whereby the temperature of this Heizraumes raised and thus an increase in the heating of the charge is effected from below. Finally, it is also possible to use the ceiling openings of the coke oven chamber for heating. Even a wall-heated type of coke oven, as disclosed, for example, in US Pat. No. 4,045,299A, is conceivable for execution, although it has not been tested for the present invention. The heating can be adjusted by way of example with the aeration and pressure control of the coke oven chamber, that sets an overpressure of 0.01 to 20 mbar in the coke oven chamber. This can be achieved by an appropriate regulation of the burner and the ventilation flaps. In a preferred embodiment of the invention, the heating is adjusted with the aeration and pressure control so that an overpressure of 0.1 to 10 mbar is established in the coke oven chamber.

For heating the coke oven chamber, for example, natural gas can be used as the heating gas. For heating the coke oven chamber but also liquefied petroleum gas, coke oven gas, blast furnace top gas, or converter gas can be used as heating gas. For carrying out the method according to the invention, it is also possible to use for heating a mixture of at least two gases from the group of gases natural gas, liquid gas, coke oven gas, blast furnace direct gas or converter gas in any proportion. The choice of a suitable heating gas depends on various factors such as availability.

The adjustment of the volatiles content in the petroleum carbonated is important to achieve the desired CSR strength and CRI reactivity of the coke product, and to ensure a desired heatability with the heating power through the outgassing components. In one embodiment of the invention, the petroleum-based coal mixture is mixed with coal as an additive before grinding, so that a volatiles content of between 19 and 25 percent by weight, based on the dry starting mixture, is established. In a further embodiment, the petroleum-based coal mixture is mixed with bitumen as an additive before grinding, so that a volatiles content of between 19 and 25 percent by weight, based on the dry starting mixture, is established. In another embodiment, the petroleum coke mixture is mixed before grinding with an oil type as an additive, so that a volatile content between 19 and 25 percent by weight, based on the dry starting mixture, sets. The resulting coke product has a CSR strength greater than 44% and a CRI reactivity of less than 33%.

The petroleum used also has, due to the process steps in which this is obtained, an ash content which is less than 2 percent by weight. This is usually just enough to protect the petroleum coking from coking from excessive combustion. However, in order to ensure sufficient cost-effectiveness of the process, it is often necessary to additional measures to take before an undesirable burning of petroleum coke. It is also possible to select the content of volatile constituents slightly higher if the petroleum coals are admixed with additives which have an inhibiting effect on the combustion of the petroleum coals. The ash content can be selected higher, if the petroleum is added to an additive that exerts an influence on the burning behavior of petroleum. The ash content has the task of avoiding an undesirable combustion of the petroleum coals. In one embodiment of the invention, the petroleum blend is added with ash additive so that the ash content is adjusted between 2 and 12 weight percent, preferably 2 to 6 weight percent, based on the total dry mix, and this mixture is ground and sized, a fraction with a particle size distribution d of 0.5 <d <3 mm is obtained, and the classified mixture for further coking in the coal storage bunker or coal storage container is given. Milling and classifying is necessary to distribute the ash in the product so that the achieved CSR strength and CRI reactivity are not adversely affected.

In a further embodiment, the petroleum-carbon mixture is mixed with ash-containing coal as an additive, so that the ash content is adjusted between 2 and 12 percent by weight, preferably 2 to 6 percent by weight, based on the total dry mixture, and this mixture is ground and classified, wherein a fraction having a particle size distribution d of 0.5 <d <3 mm is obtained, and the classified mixture is added to the coal storage bunker or coal storage container for further coking. The petroleum-based coal mixture can also be ground completely or partially in a milling apparatus before admixing the additives or after admixing the additives, so that an average grain size of the residue fraction of less than 3 mm results. The grinding process can also be carried out for a partial fraction of the total mixture. Partial fractions of from 70 to 95 parts by weight and more preferably from 80 to 90 parts by weight are preferred. It is within the scope of the invention also possible to change the water content of the petroleum charcoal used by adding water. The addition of water can improve the stability of the petroleum coarse cake. In one embodiment of the invention, the total water content of the feed mixture is adjusted to 7 to 11.5% by weight by adding liquid water, and this mixture is added to the coal storage bunker or coal storage container for further coking. The addition of the water can be done directly, but also by spraying or dipping.

The feed mixture can be compacted in the context of the invention before use with any type of compression device, so that the density of the feed mixture is 0.8 t / m ³ to 1, 225 t / m ³ . The compaction process can generally be carried out by pressing, stamping, hammering or shaking procedures, which can also be used in combination. Preferably, the feed mixture is compacted prior to use with a stamping device so that the density of the feed mixture is 1, 0 t / m ³ to 1, 150 t / m ³ . To influence the coking process, a combustion-inert separating layer can be applied to the surface of the Ofenbesatzes before the start of heating. This example consists of coke. In a further embodiment, this combustion-inert separating layer consists of carbon. Finally, this combustion-inert separating layer can also consist of ash or sand. Finally, this combustion-inert carbonaceous grit separation layer can be, for example, charcoal or coke breeze having a grain size of less than 25 mm.

In one embodiment of the invention, the layer thickness of the separating layer is 0.2 cm to 25 cm. The separating layer can be applied as desired. Thus, for example, it is possible to apply the release layer to the coal compact with a carbon compacting machine containing an addition port located on or between the punches. For this purpose, a Kohlekompaktiereinrichtung is required, which contains at least one stamp with an addition device above the batch. Coal compacting machines provided with stamping, hammering, shaking and pressing devices for compaction are prior art and are exemplified in WO2010102714A2.

In a further embodiment, the additive is stored in the coal storage bunker in a special shaft from which when loading the compactates of the additive is added to the designated opening of the coal compacting machine. The addition of the additive can be done in the designated opening of the coal compacting by means of a screw conveyor. The addition of the additive in the designated opening of the coal compacting can thus also be done by means of a slide system, a chain conveyor system, a free-fall or a slide. The release layer can also be be heaped up on the surface of the batch outside of the compacting device.

In a further embodiment of the invention, the feed mixture with the additives in four successive mixing bunkers, in which a grinding and mixing of the ground material takes place, mixed. The grinding and mixing can also be done in several stages. The feed mixture can also be preheated. For example, it is possible to adjust the temperature of the feed mixture by pre-heating to 120 to 250 ° C. in a heatable container prior to filling in the coke oven.

The resulting metallurgical coke from the petroleum can be used arbitrarily. In particular, this can be used as blast furnace coke. However, it can also be used in non-ferrous metallurgy for the production of metals or for the production of electrodes.

Also claimed is a device with which the method according to the invention can be carried out. In particular, a coke oven for producing coke from petroleum coal obtained in the petroleum-processing industry is claimed

• built according to the construction principle of a 'non-recovery' or 'heat-recovery' coke oven bank, which has a coke oven chamber width of 2 to 6 meters and a coke oven chamber length of 10 to 20 meters, so that at a height of 2 meters the volume of the coke oven bank Coke oven chamber is 40 to 240 m ³ , and

 • the coke oven has a masonry vault vertex, which is able to form with the underlying coke oven chamber in the filled state above the coal cake gas space as a primary boiler room, and

 • the coke oven is equipped with side exhaust ducts and a secondary heating space below the coal, and

 The coke oven chamber is equipped with a coal storage bunker or coal storage container and a filling machine capable of filling the coke oven chamber from the coal storage bunker or coal storage container, and characterized in that

• the coke oven chamber is heated with external burners, which heat the primary heating room, and the burners are connected via manifolds long of the coke oven chamber front and controllable branch lines are fed into the burner with a fuel gas and an oxygen-containing gas.

The external burners may be arranged arbitrarily on the coke oven chamber to allow heating of the Primärheizraumes. These can be arranged individually or in multiples per coke oven chamber. However, in a preferred embodiment, the burner (s) are located on at least one side of the coke oven chamber in the coke oven chamber wall above the coke oven chamber door, and heat the primary boiler room through an opening located in the coke oven door wall. Through this opening, the mouth segment of the combustion tube is guided into the gas space.

For this sit the burner or burners on at least one side of the coke oven chamber in the coke oven chamber wall over the coke oven chamber, and heat the Primärheizraum through a located in the coke oven chamber wall comprehensive opening, in an advantageous embodiment, a vertical distance between the combustion pipe mouth and the top of the petroleum coal charge is set more than 100 mm. An arrangement of the burner on the ceiling of the coke oven chamber, in turn, saves space.

In one embodiment of the invention, the burner tube mouth or the burner tube mouths made of a heat-resistant steel. In a further embodiment, the burner pipe mouth or the burner pipe mouths consists of a refractory ceramic material. This may be present on one or more burners when a plurality of burners are installed.

In a preferred embodiment of the invention, the coke oven according to the invention is combined with a further plurality of coke ovens to form a coke oven bank, and the collecting line runs along the coke oven chamber front of the coke oven bank. The summary of coke ovens of the type "non-recovery" or "heat recovery" coke oven benches is familiar to the expert for coking technology. Also, the Sekundärheizraum can be heated with one or more external burners, which are supplied via a manifold along the Koksofenkammerfront with a fuel gas and an oxygen-containing gas, with controllable branch lines open into the burner. In one embodiment of the invention The burner is designed as a fan burner. The manifold may be exemplified on the coke oven chamber ceiling for execution. The collecting line can also be mounted below the platform for the coke oven operating machine or along the anchor stands. Finally, the manifold can be arranged arbitrarily to ensure the supply of the burner or the.

The control of the branch line or the branch lines can be done by way of example via a cock, a slide, a nozzle, a flap or a diaphragm. In one embodiment of the invention, the coke oven bank includes a pressure regulating station in which the heating gas is throttled to the required pressure so that it is fed from the pressure regulating station via the manifold into the burners, and is provided directly for the burners with the correct pressure.

Also claimed is a compacting device for compaction of coal, which is suitable for applying a release layer on Kohlekompaktate in the production of Kompaktate. A suitable compacting device, which can be used to manufacture this device, describes the teaching WO2010102714A2. This consists of six punches, which are used as side surfaces in the formation of compacts by a pressing device. The punches are operated hydraulically in one embodiment of the invention. A suitable compacting device can also be formed from a vibrating device. To form the compacting device according to the invention, the upper punch or the upper plate of the vibrating device of the compacting device from WO2010102714A2 is provided with a pouring device, through which an additive can be added to the surface of the compactate, so that on the surface of the compacted feed mixture during compacting further layer of added by the shaking additive forms.

Also claimed is a coke oven bank, which is constructed from the coke ovens according to the invention, and which is equipped with this compacting device.

The method according to the invention is mainly used in coke oven benches, which are formed from the coke oven chambers according to the invention with additional devices from the prior art. These include, for example, 1 to 10 bunkers in which the various petroleum-charcoal feed mixtures are stored. These include, for example, 1 to 4 grinding devices, 1 to 4 sieving devices, or 1 to 4 mixing bins, in which the petroleum coke, the additives stored or classified, or mixed, the total feed mixture. The coke oven banks can also be provided with a compacting device.

The invention has the advantage of providing petroleum coke, which is a petroleum coke fraction having a volatiles content of 15 to 19% by weight, to petroleum coke and petroleum refining industry to provide an economical use by making therefrom a coke containing a CSR Has a strength of more than 44% and a CRI reactivity of less than 33%, so that it can be used in a blast furnace process or in smelting processes for the production of metals, in contrast to coked Petroikoks.

Examples

In the following, analytical methods are described for petroleum coke, which serve to provide a petroleum charcoal, which acts as Ausgangsspetrolkohle for the inventive method. Volatile matter. The determination of the volatiles content of the petroleum coke is carried out by way of example according to DIN 51720. The proportion of the residue which remains after heating the coal within 7 minutes at 900 ° C under vacuum. A method for the rapid determination of the volatiles content of coal is US6074205A. 2. ash content. The determination of the ash content is carried out by way of example according to DIN 51719. The proportion of the residue which remains after combustion of the coal in the furnace at 815 ° C is measured. A method for the rapid determination of the ash content in coal is DE3120064A1.

3. Strength of the coke. The strength of coke is determined by the so-called CSR test. CSR stands for the English term "Coke Strength after Reaction." The percentage weight of the residue, which is obtained from a 200 g test block of coke after heating under 1 bar of carbon dioxide (CO ₂ ) for 2 hours at 1 100 ° C. and the following Treatment in a rotary drum at 600 revolutions per minute (min ^"1 ) for 30 minutes is obtained. This test method is generally accepted today, is standardized and is described by way of example in EP0738780B2.

4. Reactivity of the coke. The reactivity of coke is determined by the so-called CRI test. CRI stands for the English term "Coke Reactivity Index" and describes the chemical reactivity of the coke, which measures the percentage by weight of the residue obtained from a 200 g test block of coke after heating under 1 bar of carbon dioxide (CO ₂ ) for 2 The value obtained is called CRI reactivity The smaller the value obtained, the lower the reactivity This method is simple and quick to carry out and the characteristic CRI allows a good correlation with the behavior of the coke This test method is now generally accepted, is standardized by ISO 18894, and is described by way of example in EP1142978A1.

Claims

Patent claims 1. Process for the production of metallurgical coke from petroleum coal produced in the petroleum processing industry, whereby • Petrocoke from petrochemical processes is subjected to volatile and ash analysis so that it can be sorted into batches with a known volatile and ash content, and • a batch of petroleum coal with a volatile content of 15 to 19 percent by weight and an ash content of less than 2 percent by weight, based on the water- and ash-free batch of petroleum coal, is sorted out and placed in a coal storage bunker or coal storage container, and • this petroleum coal fraction from the coal storage bunker or coal storage container is first fed into a compacting device for compression by filling machines and then into a coke oven with the dimensions of the “non-recovery” or “heat-recovery” type for cyclic coking, characterized in that • the coke oven is equipped with at least one externally heated burner for heating the primary heating space above the petroleum coal cake or for heating the secondary heating space below the coke oven chamber or both, through which the petroleum coal in the coke oven chamber is heated with a heating gas to a temperature of 1000°C to 1550°C is heated within a period of less than 120 hours, so that a metallurgical coke with a CSR strength value of at least 44% and a CRI reactivity value of less than 33% is obtained. 2. The method according to claim 1, characterized in that the volatile content of the petroleum coal before coking is 16 to 18 percent by weight. 3. Method according to one of claims 1 or 2, characterized in that the Heating in the coke oven is carried out by introducing the burner flame into the gas space above the petroleum coal charge. 4. The method according to any one of claims 1 to 3, characterized in that the coke oven is equipped with at least one externally heated burner for heating the secondary heating space below the petroleum coal cake, through which the petroleum coal cake is heated. 5. The method according to claim 4, characterized in that the heating in the coke oven is carried out by introducing the burner flame into the gas space below the petroleum coal charge. 6. The method according to one of claims 1 to 5, characterized in that the heating is adjusted with the ventilation and pressure control so that an overpressure of 0.01 to 20 mbar is established in the coke oven chamber. 7. The method according to one of claims 1 to 5, characterized in that the heating is adjusted with the ventilation and pressure control so that an overpressure of 0.1 to 10 mbar is established in the coke oven chamber. 8. The method according to any one of claims 1 to 7, characterized in that natural gas is used as heating gas for heating. 9. The method according to any one of claims 1 to 7, characterized in that liquid gas is used as heating gas for heating. 10. The method according to any one of claims 1 to 7, characterized in that coke oven gas is used as heating gas for heating. 1 1. Method according to one of claims 1 to 7, characterized in that blast furnace gas is used as heating gas for heating. 12. The method according to any one of claims 1 to 7, characterized in that converter gas is used as heating gas for heating. 13. The method according to any one of claims 8 to 12, characterized in that a mixture of at least two gases from the group of gases natural gas, liquid gas, coke oven gas, blast furnace top gas or converter gas is used in any proportion for heating. 1 . Method according to one of claims 1 to 13, characterized in that the petroleum coal mixture is mixed with hard coal as an additive before grinding, so that a volatile content of between 19 and 25 percent by weight, based on the dry feed mixture, is achieved. 15. The method according to any one of claims 1 to 13, characterized in that the petroleum coal mixture is mixed with bitumen as an additive before grinding, so that a volatile content of between 19 and 25 percent by weight, based on the dry feed mixture, is achieved. 16. The method according to any one of claims 1 to 13, characterized in that the petroleum coal mixture is mixed with a type of oil as an additive before grinding, so that a volatile content of between 19 and 25 percent by weight, based on the dry feed mixture, is achieved. 17. The method according to one of claims 1 to 16, characterized in that the petroleum coal mixture is mixed with ash as an additive so that the ash content is set between 2 and 12 percent by weight, based on the dry total mixture, and this mixture is ground before coking and classified, whereby a fraction with a grain size distribution d of 0.5 <d <3 mm is obtained, and the classified mixture is placed in the coal storage bunker or coal storage container for further coking. 18. The method according to one of claims 1 to 16, characterized in that the petroleum coal mixture is mixed with ash-containing coal as an additive so that the ash content is set between 2 and 12 percent by weight based on the dry total mixture, and this mixture is ground before coking and classified, whereby a fraction with a grain size distribution d of 0.5 <d <3 mm is obtained, and the classified mixture is placed in the coal storage bunker or coal storage container for further coking. 19., Method according to claim 18, characterized in that the petroleum coal mixture is mixed with ash-containing coal as an additive so that the ash content is set between 2 and 6 percent by weight based on the dry total mixture, and this mixture is ground and classified before coking , whereby a fraction with a grain size distribution d of 0.5 <d <3 mm is obtained, and the classified mixture is added to the coal storage bunker or coal storage container for further coking. 20. The method according to one of claims 14 to 19, characterized in that the petroleum coal mixture is also ground completely or partially in a grinding device before or after the additives have been added, so that an average grain size of the residue fraction of less than 3 mm results. 21. The method according to any one of claims 1 to 20, characterized in that the total water content of the feed mixture is adjusted to 7 to 11.5 percent by weight by adding liquid water, and this mixture is added to the coal storage bunker or coal storage container for further coking. 22. The method according to one of claims 1 to 21, characterized in that Before use, the feed mixture is compacted with a compaction device so that the density of the feed mixture is 0.8 t/m ³ to 1.225 tm ³ . 23. The method according to any one of claims 1 to 21, characterized in that the feed mixture is compacted with a stamp device before use, so that the density of the feed mixture is 1.0 t/m ³ to 1.150 t/m ³ . 24. The method according to any one of claims 1 to 23, characterized in that before the start of heating, a combustion-inert separating layer is applied to the surface of the furnace trim. 25. The method according to claim 24, characterized in that this combustion-inert separating layer consists of coke. 26. The method according to claim 24, characterized in that this combustion-inert separating layer consists of coal. 27. The method according to claim 24, characterized in that this combustion-inert separating layer consists of carbon-containing grit with a grain size of less than 25 mm. 28. The method according to claim 24, characterized in that this combustion-inert separating layer consists of ash or sand. 29. The method according to any one of claims 24 to 28, characterized in that the layer thickness of the separating layer is 0.2 cm to 25 cm. 30. The method according to any one of claims 24 to 29, characterized in that the separating layer is applied to the coal compact with a coal compacting machine which contains an addition opening provided for this purpose on the upper stamp or the upper plate. 31. The method according to one of claims 24 to 30, characterized in that the additive is stored in the coal storage bunker in a special shaft from which the additive is added to the opening provided for this purpose in the coal compacting machine during loading. 32. The method according to claim 31, characterized in that the additive is added into the opening provided for this purpose in the coal compacting machine by means of a screw conveyor. 33. The method according to claim 31, characterized in that the additive is added into the opening provided for this purpose in the coal compacting machine by means of a slide system. 34. The method according to claim 31, characterized in that the additive is added into the opening provided for this purpose in the coal compacting machine by means of a chain conveyor system. 35. The method according to any one of claims 24 to 34, characterized in that the feed mixture is mixed with the additives in up to four successive mixing bunkers in which multi-stage grinding and mixing of the ground material takes place. 36. The method according to any one of claims 1 to 35, characterized in that the temperature of the feed mixture is preheated to 120°C to 250°C in a heatable container before filling into the coke oven. 37. Coke oven for producing coke from petroleum coal produced in the petroleum processing industry, which • is constructed according to the construction principle of a “heat recovery” coke oven bank, which has a coke oven chamber width of 2 to 6 meters and a coke oven chamber length of 10 to 20 m, so that at a height of 2 m, the volume of the coke oven chamber is 40 to 240 m ³ is, and • the coke oven has a brick vault, which, together with the coke oven chamber underneath, can form a gas space above the coal cake as a primary heating space when filled, and 5 · the coke oven is equipped with side exhaust ducts and a secondary heating room underneath, and • the coke oven chamber is equipped with a coal storage bunker or coal storage container and a filling machine which can fill the coke oven chamber from the coal storage bunker or coal storage container, i o characterized in that • The coke oven chamber is heated with external burners, which heat the primary heating space, and the burners are supplied with a heating gas and an oxygen-containing gas via manifolds along the coke oven chamber front and controllable branch lines into the burners. 15 38. Coke oven according to claim 37, characterized in that the burner or burners sit on at least one side of the coke oven chamber in the wall surrounding the coke oven chamber door above the coke oven chamber door, and heat the primary heating space through an opening located in the wall surrounding the coke oven chamber door, with a vertical Distance between the burner tube mouth and the top !0 edge of the batch of more than 100 mm is set. 39. Coke oven according to one of claims 37 or 38, characterized in that the burner tube mouth consists of a heat-resistant steel. 40. Coke oven according to one of claims 37 or 38, characterized in that the burner tube mouth consists of a fireproof ceramic material. !5 41. Coke oven according to one of claims 37 to 40, characterized in that the Coke oven is combined with a further plurality of coke ovens to form a coke oven bank, and the collecting line runs along the coke oven chamber front of the coke oven bank. 42. Coke oven according to one of claims 37 to 41, characterized in that i0 the secondary heating room is also heated with an external burner, and this is supplied with a heating gas via a manifold along the coke oven chamber front is supplied with an oxygen-containing gas, which flows into the burner via an adjustable branch line. 43. Coke oven according to one of claims 37 to 42, characterized in that the burner or burners are designed as forced-air burners. 44. Coke oven according to one of claims 37 to 43, characterized in that the collecting line is located on the coke oven chamber ceiling. 45. Coke oven according to one of claims 37 to 44, characterized in that the collecting line is located below the platform for the coke oven operating machine. 46. Coke oven according to one of claims 37 to 45, characterized in that the control of the branch line or the branch lines takes place via a tap, a slide, a flap, a nozzle or a diaphragm. 47. Coke oven according to one of claims 37 to 45, characterized in that the coke oven bank contains a pressure control station in which the heating gas is throttled to the required pressure and is thus fed into the burners from the pressure control station via the collecting line. 48. Compacting device for compacting coal, which consists of up to eight stamps, the stamps being used to form compacts by a compacting device, characterized in that the compacting device contains a pouring device through which an additive is added to the surface of the compacted material can, so that a further layer of an additive added by the pouring device forms on the surface of the compacted feed mixture during compaction. 49. Compacting device for compacting coal according to claim 48, characterized in that the compacting device for forming compacts contains a hydraulic pressing device. 50. Compacting device for compacting coal according to claim 48, characterized in that the compacting device, which is used to form compacts, is formed by a shaking device. 51. Coke oven bench according to one of claims 37 to 50, characterized in that it is equipped with a compacting device according to one of claims 48 to 50.