RU2616473C2 - Method and device for furnace coke production from petroleum coke, produced at reforming plants by coking in ''non-recuperative" coke ovens or coke ovens "with heat recuperation" - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: in the method the petroleum coke is analyzed for ash and volatile matters content. The portion of petroleum coke, received by screening, has the volatile matters content 15-19 wt % and the ash content upto 2 wt %. This fraction of petroleum coke is compacted and placed in the coke oven for the cyclic carbonization. The coke oven is equipped with at least one burner with external heating to heat the space of the primary heating over the petroleum coke cake or the secondary heating space below the coke oven chamber or both. Th petroleum coke is heated upto the temperature of 1000-1550°C during less than 120 hours. The resulting blast furnace coke has a durability index of CSR at least 44% and the index of reactivity CRI less than 33%.

EFFECT: production of coke, which has a higher strength and low reactivity and suitable for use as a blast furnace coke.

16 cl

Description

[0001] The invention relates to a method for the production of blast furnace coke from petroleum coke obtained in crude oil refineries by coking in "non-regenerative" coke ovens or "heat recovery" coke ovens, starting from petroleum coke obtained or produced in plants according to processing of crude oil and having initially a volatile content of 15-19 mass. % and ash fraction up to 2 wt. %, moreover, this petroleum coke is introduced in a compacted form into a coke oven of a "non-regenerative" design or a "heat recovery" design for cyclic coking, moreover, said furnace is equipped with at least one burner with external heating, and the primary heating space or space secondary heating below the coke oven chamber or both are heated to a temperature of 1000-1550 ° C, and for a period of time less than 120 hours, the fraction of volatiles present in petroleum coke is completely degassed, giving a blast furnace coke having a CSR strength of at least 44% and a CRI reactivity of less than 33%, both of which are suitable for use as blast furnace coke. In addition, the invention relates to a coke oven designed in accordance with the principle of “non-regenerative” coke ovens or “heat recovery” coke ovens, and comprising a primary heating space equipped with burners heating the primary heating space.

[0002] Products of the processing of petroleum products and crude oil in plants for the formation of crude oil products include not only the required products, but also a product known as petroleum coke, which is formed from high-boiling residues in rectification operations, in reforming stages, in hydrogenation processes and refining operations at a crude oil refinery. This petroleum coke usually consists of more than 88 mass. % carbon with a volatile content (VOC) of 8-12 mass. % This petroleum coke is of little economic interest, possessing properties that are undesirable with respect to numerous value-adding operations, such as, for example, low CSR strength and high CRI reactivity, and therefore cannot find suitable consumer markets.

[0003] Petroleum coke is often used in applications such as, for example, metallurgy for the manufacture of electrodes. The use of petroleum coke in the production of pig iron and steel, i.e., for example, as a reducing agent in the operation of a blast furnace for the production of pig iron, is impossible, since the strength of petroleum coke is insufficient for use in a blast furnace. Additionally known is the mixing of petroleum coke fractions with a mixture of bituminous coal, but the mixed petroleum coke fraction is limited to orders of magnitude less than 10 masses. % due to the low quality of blast furnace coke obtained from it.

[0004] Another problem with petroleum coke is impurities coming from the processing of crude oil and accumulating in petroleum coke during its removal. The impurities often found in petroleum coke are, for example, vanadium, nickel, sulfur, silicon, iron or titanium. For example, the vanadium content in fractions of petroleum coke can be up to 0.17 mass. %, nickel content up to 0.04 mass. %, and sulfur content up to 5 mass. % The consequence of the presence of these impurities is that petroleum coke cannot be used directly for heating purposes, since doing so would mean polluting the environment. Another characteristic of petroleum coke is that it has a lower flame temperature than blast furnace coke or coal. As for its use as a fuel and its handling, this is an undesirable feature that excludes the possibility of its use for numerous further processing operations. Therefore, a search is underway for ways to ensure the economic prospects for the use of petroleum coke.

[0005] A significant obstacle to the production of blast furnace coke by adapting the coking process in accordance with the properties of petroleum coke, in addition to impurities and the lack of strength of the product, is, in turn, the fluctuating proportion of volatile constituents. A consequence of the fluctuating fraction of volatile constituents is that the use in a coke oven is difficult to control due to the essentially inaccurate heating properties arising from the volatile constituents. In fact, the main fraction of petroleum coke obtained at refineries has a very low fraction of volatile constituents, less than 19 mass. %, the consequence of which is that when used in a "non-regenerative" coke oven or coke oven "with heat recovery" coke is not suitable for providing a process of self-sustaining combustion and, therefore, coking. In the case of the exclusive use of petroleum coke as a starting material in this coke oven, the coking operation after several coking cycles will then practically stop, since the heat generated by the combustion of volatile constituents during coking and stored in the refractory material of the furnace will no longer be sufficient to maintain the furnace temperature at the required high above 1000 ° C on subsequent downloads.

[0006] Another difficulty affecting its coking is that, during the coking process, petroleum coke exhibits very high expansion pressures due to the presence of low boiling volatile constituents therein. During the coking process, these components lead to a significant increase in the volume of coke cake, corresponding to almost expansion. Therefore, it is impossible to coke petroleum coke in a conventional coke oven, since during the coking process the walls of the coke oven chamber will certainly be damaged as a result of the increase in the volume of coke cake. This increase in the volume of petroleum coke cake, due to the indicated properties of the petroleum coke cake, also has the consequence that the coke product obtained using petroleum coke fractions in a tar tar mixture is very difficult to forcibly remove from the chamber of a conventional coke oven.

[0007] One possibility of processing and further use of petroleum coke is described in document WO 0010914 A1. This document proposes the process of exposing petroleum coke from crude oil refineries derived from petroleum coke precursor material from petroleum products, thermal cracking operations at a sufficiently high temperature and for a sufficiently long period of time to produce petroleum coke containing a reduced and precisely controlled content volatile substances 13-50 mass. % In addition, the process describes the possibility of desalting petroleum coke to remove metallic impurities that it contains. Finally, this document describes the ability to select sulfur impurities in petroleum coke to a reduced and environmentally acceptable fraction by, for example, adding desulfurizing additives to the fluidized bed. The process makes it possible to obtain petroleum coke fractions having a very precisely defined content of volatile constituents and impurities. Petroleum coke fractions having a volatile content of 15-25 mass. %, are referred to here as petroleum coke, but also duplicated as “petroleum coal”, since their properties resemble those of ordinary bituminous greasy or blacksmith coals.

[0008] In the document D.N. Walker et al., "Sun Coke company heat recovery cokemaking technology high coke quality and low environmental impact", Revue de metallurgie - Cahiers d'informations techniques, Revue de metallurgie, Paris, France, Volume 100, No. 3, 1 March 2003, pages 233-241, III, V, XP008123362, ISSN: 0035-1563 describes a plant for the production of coke, which produces coke starting from various grades of coal, while coke, depending on the type of coal used, has certain stability and a certain fraction of volatile constituents, and the installation consists of coke ovens that contain coke oven chambers with downward channels, a corresponding furnace bottom, a coke oven stove, and one or more upward channels for flue gas, and also a channel for flue gas split women on the coke oven chamber, a spare exhaust pipe, a vessel for use with an associated waste heat generating set, and installation for flue gas cleaning with exhaust pipe for the exhaust gases downstream.

[0009] WO 2011054421 A1 describes a method for retaining heat in the chambers of a coke oven while the vessel is idle to use excess heat, while the coke oven chambers are kept warm by means of burners with external heating during the idle time after discharge, thereby flue gas with low pollutants are obtained from these burners, so that vessels for using excess heat, which during normal operation cool the flue gases from the batteries of the space stoves and use them to generate steam, can be Opened and inspected, and the operation of the burners produces flue gas with a low content of pollutants, which can be discharged directly into the atmosphere.

[00010] Document WO 2007149642 A2 describes a method for increasing the packing density of a coal briquette consisting of coal particles in order to create an extended layer of dry compacted coal for filling into a coke oven, said method comprising the steps of unloading a coal briquette onto a loading plate that contains the side walls and is located outside the coke oven, while the loading plate contains at least one movable end side, in order to place the upper surface of the dry sealed coal seam over the loading with a hot plate and applying pressure to the upper surface of the coal briquette to degass the coal, and thereby produce a layer of dry compacted coal, which has a loading density in the range of from about 960 to about 1200 kilograms per cubic meter, which can be introduced into the coke oven for coking by means of a loading plate.

[00011] US Pat. No. 6,290,494 B1 describes a coke oven filling machine comprising a movable frame and a coke oven feeding device that includes a movable elongated loading plate having a first end wall and a second end wall, and retractable side walls on the loading plate, and transition section at the first end of the loading plate, which can form a movable area between the first end of the loading plate and the coke oven, while the loading plate is equipped with a drive unit for moving the loading plate you into the coke oven, so the coke oven loading machine provides the ability to quickly load the coke oven with a compacted coke charge, even allowing the use of low-grade coal for the production of blast furnace coke.

[00012] US 2787585 A describes a method for producing blast furnace coke from highly volatile, poorly coking coal, from which under normal conditions coke is obtained having insufficient strength for metallurgical applications, the method comprising mixing a relatively large fraction of coal having a high content volatiles in the range of approximately 7-25 mass. %, and petroleum coke having a volatile content in the range of about 14-24 mass. %, and exposing the mixture to temperatures that are commonly used for coking coal until the coal is fully coked, to produce blast furnace coke, which has increased strength relative to coke produced only from coal having a high fraction of volatile substances.

[00013] US 2640016 A describes a method for producing blast furnace coke, for which an initial mixture is first produced, which consists of highly coking coal having a high fraction of volatiles, and petroleum coke having a fraction of 5-25 percent, while petroleum coke has a fraction of volatile substances in the range of 14-35 percent, determined in accordance with ASTM method No. D271-48, modified for peat and brown coal, and consists exclusively of a volatile substance having a reservoir temperature in the range of 400-500 ° C, and the main fraction of finely divided solid particles in the mixture have a particle size classification of less than 1/8 inch, so that during coking a narrow, deeply passing coking zone is formed, and this mixture is coked by indirect heating at a temperature of 982-1204 ° C, while during the process a dense, solid and lumpy coke, when the initial mixture is heated in accordance with the established method.

[00014] In G. Veit, "Compacted charging: A process for economical coke making", 2nd international meeting on ironmaking and 1st international symposium on iron ore and parallel event - 5th Japan-Brazil symposium on dust processing energy-environment on metallurgical industries - 2nd international meeting on ironmaking and 1st int., Volume 2, 2004, pages 1231-1240, XP08162957 describes in a review article the advantages of compaction of various types of coal, used not only for traditional coke ovens that capture volatile coking products for further processing, and for non-regenerative coke ovens that use volatile coking products for heating by combustion I, at the same time, the compaction operation provides the CSI strength of coke of more than 65, and it is possible to produce high-quality coke even from low-calorie coal, petroleum coke and metallurgical coke, despite the appropriate choice of the types of initial coal, and the compaction process for non-regenerative coke ovens is carried out in a compaction apparatus for the purpose of creating a uniform coking coal mass consisting of coked coal which has the same length and Irina, that the coke oven chamber.

[00015] The presence of petroleum coke with a precisely defined fraction of volatile constituents and impurities opens up new possibilities for using the resulting petroleum coke for the production of blast furnace coke. The processing of crude oil gives a particularly high fraction of petroleum coke having a volatile content of 15-19 mass. % To date, this product has not undergone further processing on an industrial scale, since conventional coking processes do not solve the problems associated with this product: low energy content, low economy, dangerous swelling pressures during coking, significant pollution and high heating losses. However, laboratory studies of blast furnace coke obtained from this particular fraction of petroleum coke indicate its high quality. Examples of these studies are provided 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 blast furnace coke from petroleum coke has not yet been ensured, there is a need to obtain a feasible method for the production of blast furnace coke by coking petroleum coke in a coke oven.

[00016] Therefore, the aim of the invention is to provide a method that allows you to get petroleum coke with a fraction of 15-19 mass. % volatile constituents and an increased fraction of impurities, it is used for coking on an industrial scale and receives coke from it, which has increased strength and low reactivity and is suitable for use as blast furnace coke.

[0017] The goal is achieved in accordance with the present invention by a method in which petroleum coke is taken having a known volatile content of 15-19 masses. % and the known ash fraction up to 2 mass. %, and then carry out the coking of this petroleum coke in a compacted form under regular conditions with temperatures in the heating chambers 1000-1550 ° C for a period of 120 hours in a "non-regenerative" coke oven or coke oven "with heat recovery" to produce blast furnace coke, moreover, the furnace is equipped with at least one burner for heating the primary heating space formed by the gas space present when working on a cake of petroleum coke, or for heating the secondary heating space below the coke oven chamber echi, or both.

[0018] The volatiles content and the petroleum coke ash content are determined by analysis before coking, it does not matter where the analysis is performed: at the site where the coke oven is located, or at the site of the petroleum coke supplier. All that is important for the implementation of the proposed method is that there is petroleum coke having a known content of volatile components, the limits of which should be at least 15 mass. % and not more than 19 mass. %

[0019] In order to compensate for the reduced energy content due to the lower fraction of volatile constituents of petroleum coke having these properties, it is necessary to use an external heating gas to heat the primary heating space or the secondary heating space, since the goal is to only further process it this low-energy petroleum coke fraction to produce blast furnace coke in a non-regenerative coke reactor or recuperation coke th heat. Otherwise, the consequence would be a disproportionately long and uneconomical coking time, since the low energy content of the feedstock is not sufficient to sustainably maintain temperatures above 1000 ° C and so that to compensate for the high heat loss with exhaust gases and radiation heat losses associated with this operation .

[0020] However, due to the use of a coke oven of a non-regenerative or heat recovery structure, it is possible to coke a charge mixture consisting mainly of petroleum coke and having the indicated characteristics, since such a design for a coke oven leaves gas space above the petroleum coke cake in operating condition, and this gas space captures the high expansion pressures created by petroleum coke. In the context of the invention, it was found that coke grades thus obtained have CSR strengths of more than 44%, CRI reactivity indices of less than 33%, which makes it possible to use them as blast furnace coke in the production of iron and steel or, for example, during operation of blast furnaces. The indicated figures for coke are beneficial for the operation of a blast furnace, if this coke is used in the operation of a blast furnace.

[0021] In particular, a method for producing blast furnace coke from petroleum coke obtained from a crude oil refining industry is claimed, in which:

- petroleum coke from petrochemical processes is subjected to analysis for volatile matter and ash content so that it can be sorted into portions with a known volatile content and ash content, and

- sorting receive a portion of petroleum coke with a volatile content of 15-19 mass. % and ash fraction of less than 2 wt. % in terms of a portion of petroleum coke not containing water and ash, and placed in a coke tank or coke storage container, and

- this fraction of petroleum coke from the coke storage tank or coke storage container is placed by loading machines, first into the sealing means for sealing, and then into the coke oven with dimensions of a “non-regenerative” design or a “heat recovery” design for cyclic coking,

and characterized in that

- the coke oven is equipped with at least one burner with external heating for heating the primary heating space above the petroleum coke cake or for heating the secondary heating space below the coke oven chamber or both, by means of which the petroleum coke in the coke oven chamber is heated with a hot heating gas to a temperature of 1000- 1550 ° C. for a time period of less than 120 hours for the production of blast furnace coke having a CSR strength of at least 44% and a CRI of less than 33%.

[0022] Coke ovens of a non-regenerative type or of a heat recovery type with primary and secondary heating spaces are known to those skilled in the art of coking technology. This type of construction is fully described, for example, in 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, Volume 76, No . 1, January 1999, pages 33-38. A coke oven battery from coke ovens suitable for coking carbonaceous feedstocks with high expansion pressures is described in WO 2011107198 A1. During the heating process, the petroleum coke cake reaches a design temperature of 900-1100 ° C. A listing and explanation of coke ovens with heat recovery and non-regenerative designs are set forth by way of example in the descriptions of US Pat. Nos. 4,344,420 A, US 4,287,024 A, US 5,114,542 A, GB 1,555,400 A or CA 2052177 C.

[0023] As a result of the heating occurring over the compacted cake of petroleum coke, petroleum coke is heated in such a way that coke of the required quality is formed with a fraction of volatile constituents in petroleum coke rising from the portion in the form of crude coking gas. Some of these waste components are burned sub-stoichiometrically to generate heat, at least periodically, in the primary heating space, initially with the addition of air. Then the mixture of partially burnt off gases is discharged through the side gas channels of the coke oven chamber and is completely burned during further combustion in the secondary heating space. Thus, as a result of the fraction of volatiles present in petroleum coke, petroleum coke is also heated from below, and as a result, with the exception of the side door zones, petroleum coke cake is heated from all sides, and a uniform coking quality is obtained.

[0024] The quality of the obtained coke can be determined as described, obtaining a CSR strength of at least 44% and a CRI of less than 33%. A prerequisite is the use of a portion of petroleum coke having a volatile content of 15-19 masses. % and ash fraction of less than 2 mass. % in terms of a portion of petroleum coke that does not contain water and ash.

[0025] It is also possible to use petroleum coke, the volatile content of which is determined with greater accuracy. In one embodiment of the invention, the volatile content of petroleum coke is 16-18 mass. % As a result, work can be managed more efficiently.

[0026] In order to implement the invention, petroleum coke cake can, in principle, be heated from all sides, thereby reaching the desired temperature. In one advantageous embodiment of the invention, the heating is carried out in a coke oven so that the burner flame is introduced horizontally into the gas space above the portion of petroleum coke, referred to as the primary heating space. To this end, in one advantageous embodiment, at least one burner tube is located in a wall above the coke oven chamber door, where hot gas or flue gas is supplied to the burner tube and is open through an opening into the gas space above the petroleum coke, thereby heating this space with hot gas. The horizontal location of the burner tubes above the batch ensures that the inflowing gas flows into the primary heating chamber above the petroleum coke cake and, as a result, direct contact between the coke surface and the combustion air and, therefore, the unwanted burnout of the supplied coke or the resulting coke is reduced. At the same time, a vertical distance of more than 100 mm is established between the introduced burner tube and the upper edge of the batch, so that the upper layers of petroleum coke do not burn.

[0027] In the context of the invention, it is also possible, for example, to heat petroleum coke by means of additional burners located in the secondary heating space below petroleum coke. In one additional embodiment, the only or simultaneous arrangement of at least one burner in the openings of the lateral ends of the secondary heating space is claimed, due to which the temperature of this heating space rises and, consequently, the heating of the portion from below is intensified. Finally, for heating, you can use the holes in the arch of the chamber of the coke oven. For the implementation is also possible the design of a coke oven with wall heating, described, for example, in the document US 4045299 A, although for the present invention it has not been tested.

[0028] The heating can be adjusted by adjusting the aeration and pressure of the coke oven chamber, for example, so as to set an overpressure of 0.01-20 mbar in the coke oven chamber. This can be achieved by adjusting the burner and aeration flaps accordingly. In one preferred embodiment of the invention, the heating is adjusted by adjusting the aeration and pressure so as to establish an overpressure of 0.1-10 mbar in the coke oven chamber.

[0029] The coke oven chamber may be heated using, for example, natural gas as a heating gas. At the same time, liquefied gas, coke oven gas, blast furnace gas or converter gas can also be used as heating gas for heating the coke oven chamber. To implement the method according to the invention for heating, you can use a mixture of at least two gases from the group of gases, including natural gas, liquefied gas, coke oven gas, blast furnace gas or converter gas, in any proportion. The selection of an appropriate heating gas depends on a number of factors, such as, for example, availability.

[0030] In order to achieve the required CSR strength and CRI reactivity, and to provide the required heatability with the heating characteristics due to the exhaust components, it is important to establish the content of volatile components in the introduced petroleum coke. In one embodiment of the invention, before grinding, the mixture of petroleum coke is mixed with bituminous coal as an aid, so that the volatile content is 19-25 mass. % in terms of dry charge mixture. In another embodiment, before grinding, the mixture of petroleum coke is mixed with bitumen as an aid, so that the volatile content is 19-25 mass. % in terms of dry charge mixture. In another embodiment, before grinding, the mixture of petroleum coke is mixed with a grade of oil as an adjuvant, so that the volatile content is 19-25 mass. % in terms of dry charge mixture. The resulting coke product has a CSR strength of more than 44% and a CRI of less than 33%.

[0031] Furthermore, as a result of the steps of the method by which it is obtained, the petroleum coke used has an ash fraction that is lower than 2 masses. % Usually this is just enough to protect petroleum coke from excessive burning due to combustion during coking. However, in order to ensure sufficient efficiency of the method, it is often necessary to take additional measures against the unwanted burning of petroleum coke. For this purpose, it is also possible to choose a slightly increased content of volatile constituents if auxiliary agents having the effect of suppressing the combustion of petroleum coke are mixed with petroleum coke.

[0032] In addition, if an auxiliary agent is mixed with petroleum coke that affects the behavior of petroleum coke burnout, the ash fraction can be selected at a higher level. The function of the ash fraction is to prevent unwanted combustion of petroleum coke. In one embodiment, ash is mixed with petroleum coke as an adjuvant to set the ash fraction in the range of 2-12 mass. %, preferably 2-6 mass. % in terms of dry total mixture, and this mixture is crushed and sorted to obtain a fraction having a particle size distribution d in the range of 0.5 <d <3 mm, and the sorted mixture for further coking is placed in a coke tank or container for coke storage. Grinding and sorting is necessary to ensure the distribution of ash in the product so that the achieved CSR strength and CRI reactivity do not deteriorate.

[0033] In a further embodiment, coal containing ash is mixed into the petroleum coke mixture as an aid to set the ash fraction in the range of 2-12 masses. %, preferably 2-6 mass. % in terms of dry total mixture, and this mixture is crushed and sorted to obtain a fraction having a particle size distribution d in the range of 0.5 <d <3 mm, and the sorted mixture for further coking is placed in a coke tank or container for coke storage. In addition, a mixture of petroleum coke before mixing auxiliary materials or after mixing auxiliary materials can be completely or partially crushed in a grinding device to obtain an average particle size for a residue fraction of less than 3 mm. The grinding operation can be performed for a partial fraction of the total mixture. Preferred partial fractions in this case are the mass fraction 70-95 and, more preferably, the mass fraction 80-90.

[0034] In the context of the invention, it is also possible to change the water content of the petroleum coke used by adding water. Adding water can increase the resistance of petroleum coke cake. In one embodiment, the total water content of the charge mixture is adjusted by adding liquid water to 7-11.5 mass. %, and this mixture for further coking is placed in a coke tank or coke storage container. Water may be added directly or, alternatively, by spraying or immersion.

[0035] In the context of the invention, the charge mixture before filling can be sealed with a sealing device of any kind, so that the density of the charge mixture is 0.8-1.225 t / m ³ . The sealing operation can usually be carried out by the steps of pressing, tamping, impact or vibration methods, which can also be carried out in combination. Preferably, before filling, the charge mixture is compacted with a tamping device to a charge mixture density of 1.0-1.150 t / m ³ .

[0036] In order to influence the coking operation, before the start of heating, a release layer inert to combustion can be applied to the furnace loading surface. This layer consists, for example, of coke. In yet another embodiment, a combustion inert separation layer consists of coal. Finally, this combustion-inert separation layer may also consist of ash or sand. Finally, this combustion-inert separation layer may consist of carbon-containing pieces in the form of, for example, lump coal or lump coke having a grain size of less than 25 mm.

[0037] In one embodiment, the thickness of the separation layer is 0.2-25 cm. The separation layer can be applied in any way. So, for example, the separation layer can be applied to the compacted coke using a machine for sealing coke containing an additional hole located on or between the rammers. This requires a coke-sealing agent that contains at least one tamper with an additional agent above the serving. Coke compacting machines equipped with rammers or percussion, vibrating or pressing compaction devices are part of the prior art and are described as an example in WO 2010102714 A2.

[0038] In yet another embodiment, the auxiliary agent is stored in a coke tank in a special shaft, from which, when the compacts are loaded, the auxiliary agent is introduced into an opening intended for this purpose in a coke compacting machine. Auxiliary means can be added to the hole designed for this purpose in the machine for sealing coke, using a screw conveyor. In addition, the auxiliary means can be added to the hole intended for this purpose in the machine for sealing coke, using a system of sliders, a chain conveyor system, free fall means or sliding means. In addition, the release layer may be dumped onto the surface of the portion later, outside the sealing means.

[0039] In yet another embodiment of the invention, the charge mixture is mixed with auxiliary means in four successive mixing silos, in which the ground material is ground and mixed. Grinding and mixing can also be carried out in several stages. In addition, the mixture can be preheated. Thus, for example, the temperature of the charge mixture before it is loaded into the coke oven can be adjusted to 120-250 ° C by pre-heating in a heated container.

[0040] Blast furnace coke obtained from petroleum coke may find any further use. In particular, it can be used as domain coke. Alternatively, it can be used in non-ferrous metallurgy for the production of metals or for the production of electrodes.

[0041] A device is also claimed in which the proposed method according to the invention can be implemented. In particular, a coke oven is claimed for producing coke from petroleum coke obtained from a crude oil refining industry, said furnace

- designed according to the principle of a battery of “non-recuperative” coke ovens or “heat recovery” coke ovens, has a chamber width in the range of 2-6 meters and a chamber length in the range of 10-20 m, so at a height of 2 m the volume of the coke oven chamber is 40 -240 m ³ , and

- the coke oven has a brick lined apex, which, together with the coke oven chamber below, can form a gas space present above the coke cake in the filled state as the primary heating space, and

- the coke oven is equipped with side channels of the exhaust gases and the secondary heating space under the coke, and

- the coke oven chamber is equipped with a coke storage bin or coke storage container and a loading machine that can load the coke oven chamber from the coke storage bin or coke storage container,

and characterized in that

- the coke oven chamber is heated by external burners heating the primary heating space, and the heating gas and oxygen-containing gas are supplied to the burners through a collection pipe along the front of the coke oven chamber and adjustable branches to the burners,

- the burner or burners are located on at least one side of the coke oven chamber, in the wall containing the coke oven chamber door, above the coke oven chamber door and they heat the primary heating space through an opening located in the wall containing the coke oven chamber door.

[0042] The external burners may optionally be located on the coke oven chamber so as to provide heating for the primary heating space. They can be placed one or more pieces per coke oven chamber. However, in one preferred embodiment, the burner or burners are located on at least one side of the coke oven chamber, in a wall containing the coke oven chamber door, above the coke oven chamber door, and the primary heating space is heated through an opening located in the wall containing the coke chamber chamber door ovens. Through this hole, a segment of the tip of the burner pipe is directed into the gas space.

[0043] For this purpose, the burner or burners are located on at least one side of the coke oven chamber, in the wall containing the coke oven chamber door, above the coke oven chamber door and heat the primary heating space through an opening located in the wall containing the coke chamber chamber door furnace, and in one advantageous embodiment, a vertical distance of more than 100 mm is established between the outlet of the burner pipe and the upper edge of the portion of petroleum coke. In turn, the location of the burners on the roof of the coke oven chamber saves space.

[0044] In one embodiment, the outlet of the burner tube or the outlet of the burner tube is made of heat resistant steel. In yet another embodiment, the outlet of the burner tube or the outlet of the burner tube is made of refractory ceramic material. This can be done on a single burner or on several burners if several burners are installed.

[0045] In one preferred embodiment of the invention, a coke oven according to the invention is connected to several additional coke ovens to form a coke oven battery, and a collection line extends along the front of the coke oven chambers of the coke oven battery. The aggregation of coke ovens of a non-regenerative type or of a type with heat recovery into a battery of coke ovens is known to a person skilled in the art of coke oven technology.

[0046] The secondary heating space can also be heated by one or more external burners, which are supplied with heating gas and oxygen-containing gas through a collection pipe along the front of the coke oven chamber and adjustable branches open to the burners. In one embodiment, the burner or burners are in the form of burners with fans. For implementation, a prefabricated pipeline can be located, as an example, on the roof of the coke oven chamber. In addition, the prefabricated pipeline may be installed below the platform for the machine for servicing coke ovens or along anchor racks. Finally, to provide power to the burner or burners, the collection pipe may be positioned arbitrarily.

[0047] The branch or branches may be controlled, for example, by means of a valve, slider, nozzle, damper or gate valve. In one embodiment of the invention, the coke oven battery comprises a pressure control station in which the heating gas is compressed to the desired pressure and in this state passes from the pressure control station through a collection pipe to the burners and is supplied directly to the burners with the correct pressure.

[0048] In addition, a sealing means for compacting coal suitable for applying a release layer to coke compacts upon receipt of compacts is claimed. Suitable sealing means that can be used to obtain this device are described in WO 2010102714 A2. The specified tool consists of six pushers, which are used as side surfaces in the formation of compacts by a pressing device. In one embodiment, the pushers are hydraulically driven. Suitable sealing means may be formed from a vibrating device. For the formation of the sealing means according to the invention, the upper pusher or the upper plate of the vibrating device of the sealing means from WO 2010102714 A2 is equipped with tipping means by which the auxiliary means can be placed on the pressing surface, so that an additional layer of auxiliary means is formed on the surface of the densified charge mixture, added by tipping agent.

[0049] In addition, a coke oven battery is claimed consisting of coke ovens according to the invention and equipped with said sealing means.

[0050] The proposed method is mainly used in coke oven batteries formed from coke oven chambers according to the invention with known auxiliary means. These tools include, for example, 1-10 bins in which various charge mixtures of petroleum coke are stored. In addition, these means include, for example, 1-4 grinding devices, 1-4 sorting devices or 1-4 mixing bins in which petroleum coke, auxiliary means or all charge mixtures are stored, sorted or mixed. Coke oven batteries can also be equipped with a sealing agent.

[0051] An advantage of the invention is to provide an economical means of using petroleum coke obtained from crude oil refineries and from the petroleum refining industry and representing a petroleum coke fraction having a volatile content of 15-19 mass. %, and obtaining coke from it having a CSR strength index of more than 44% and a CRI reactivity index of less than 33%, which makes it possible to use it, unlike coked petroleum coke, in the operation of a blast furnace or in smelting processes for metal production.

Examples

[0052] The following is a description of analytical methods for petroleum coke serving for the production of petroleum coke acting as a source petroleum coke for the method according to the invention.

[0053] 1. Volatile matter content. The volatile content of petroleum coke is determined, as an example, in accordance with DIN 51720. The measured amount is the fraction of the residue that remains after heating the coke under reduced pressure to a temperature of 900 ° C for 7 minutes. A method for quickly determining the volatiles content of coke is described in US Pat. No. 6,074,205 A.

[0054] 2. Ash content. The ash content is determined, as an example, in accordance with DIN 51719. The measured quantity is the fraction of the residue that remains after the coke is burned in the furnace at a temperature of 815 ° C. A method for quickly determining the ash content of coke is described in DE 3120064 A1.

[0055] 3. The strength of coke. The strength of coke is determined by a test known as the CSR test. The acronym CSR stands for Coke Strength After Reaction. The measured amount is the percentage weight of the residue obtained from a 200 g coke test block after heating under pressure of 1 bar of carbon dioxide (CO ₂ ) at a temperature of 1100 ° C for 2 hours, followed by treatment in a rotating drum at a speed of 600 rpm (min " ¹ ) for 30 minutes. Currently, this test method is universally recognized, standardized and described as an example in document EP 0738780 B2.

[0056] 4. The reactivity of coke. The reactivity of coke is determined by a test known as a CRI test. The acronym CRI stands for Coke Reactivity Index and describes the chemical activity of coke. The measured amount is the percentage weight of the residue obtained from a 200 g coke test block after heating under pressure of 1 bar carbon dioxide (CO ₂ ) at a temperature of 1100 ° C for 2 hours. The resulting value is called CRI reactivity. The lower the value obtained, the lower the reactivity. This method is simple and quick, and the characteristic CRI value provides a good correlation with the behavior of coke during operation of the blast furnace. This test method is currently recognized, standardized (standard ISO 18894) and described as an example in document EP 1142978 A1.

The following are preferred embodiments of the present invention:

Embodiment 1: Method for the production of blast furnace coke from petroleum coke obtained from a crude oil refining industry, wherein

- petroleum coke from petrochemical processes is subjected to analysis for volatile matter and ash content so that it can be sorted into portions with a known volatile content and ash content, and

- sorting receive a portion of petroleum coke with a volatile content of 15-19 mass. % and ash fraction of less than 2 wt. % in terms of a portion of petroleum coke not containing water and ash, and placed in a coke tank or coke storage container, and

- this fraction of petroleum coke from the coke storage tank or coke storage container is placed by loading machines, first into the sealing means for sealing, and then into the coke oven with dimensions of a “non-regenerative” design or a “heat recovery” design for cyclic coking,

characterized in that

- the coke oven is equipped with at least one burner with external heating for heating the primary heating space above the petroleum coke cake or for heating the secondary heating space below the coke oven chamber or both, by means of which the petroleum coke in the coke oven chamber is heated by heating gas to a temperature of 1000-1550 ° C for a period of time less than 120 hours to obtain blast furnace coke having a CSR strength of at least 44% and a CRI of less than 33%.

Embodiment 2: The method of Embodiment 1, characterized in that the volatile content of petroleum coke before coking is 16-18 mass. %

Option 3: The method according to any one of embodiments 1 and 2, characterized in that the heating is carried out in a coke oven with a flame of a burner, which is introduced into the gas space above a portion of petroleum coke.

Embodiment 4: A method according to any of embodiments 1-3, wherein the coke oven is equipped with at least one burner with external heating to heat the secondary heating space below the petroleum coke cake, whereby the petroleum coke cake is heated.

Embodiment 5: The method of Embodiment 4, characterized in that the heating is carried out in a coke oven with a burner flame, which is introduced into the gas space under a portion of petroleum coke.

Embodiment 6: The method according to any one of Embodiments 1-5, characterized in that the heating is adjusted by controlling aeration and pressure so that an overpressure of 0.01-20 mbar is set in the coke oven chamber.

Embodiment 7: The method according to any one of Embodiments 1-5, characterized in that the heating is adjusted by adjusting aeration and pressure so that an overpressure of 0.1-10 mbar is set in the coke oven chamber.

Embodiment 8: The method according to any one of Embodiments 1-7, wherein natural gas is used as the heating gas for heating.

Embodiment 9: The method according to any one of Embodiments 1-7, wherein liquefied gas is used as a heating gas for heating.

Embodiment 10: The method according to any one of Embodiments 1-7, characterized in that coke oven gas is used as the heating gas for heating.

Embodiment 11: The method according to any one of Embodiments 1-7, characterized in that blast furnace gas is used as the heating gas for heating.

Embodiment 12: The method according to any one of Embodiments 1-7, wherein converter gas is used as the heating gas for heating.

An implementation option 13: The method according to any of embodiments 8-12, characterized in that for heating use a mixture of at least two gases from the group of gases - natural gas, liquefied gas, coke oven gas, blast furnace gas or converter gas in any proportion.

An implementation option 14: The method according to any of embodiments 1-13, characterized in that before grinding, the mixture of petroleum coke is mixed with bituminous coal as an adjuvant, so that the content of volatile substances is in the range of 19-25 mass. % in terms of dry charge mixture.

An implementation option 15: The method according to any of embodiments 1-13, characterized in that before grinding the mixture of petroleum coke is mixed with bitumen as an aid, so that the content of volatile substances is in the range of 19-25 mass. % in terms of dry charge mixture.

An implementation option 16: The method according to any of embodiments 1-13, characterized in that before grinding, the mixture of petroleum coke is mixed with a grade of oil as an adjuvant, so that the volatile content is in the range of 19-25 mass. % in terms of dry charge mixture.

Embodiment 17: The method according to any one of Embodiments 1-16, characterized in that ash is mixed with petroleum coke as an aid to set the ash fraction in the range of 2-12 masses. % in terms of dry total mixture, and this mixture is crushed and sorted before coking to obtain a fraction having a particle size distribution d in the range 0.5 <d <3 mm, and the sorted mixture for further coking is placed in a coke tank or a coke storage container.

Embodiment 18: The method according to any one of Embodiments 1-16, characterized in that coal containing ash is mixed into the petroleum coke mixture as an aid to set the ash fraction in the range of 2-12 masses. % in terms of dry total mixture, and this mixture is crushed and sorted before coking to obtain a fraction having a particle size distribution d in the range 0.5 <d <3 mm, and the sorted mixture for further coking is placed in a coke tank or a coke storage container.

Embodiment 19: The method of Embodiment 18, characterized in that coal containing ash is mixed into the petroleum coke mixture as an aid to set the ash fraction in the range of 2-6 mass. % in terms of dry total mixture, and this mixture is crushed and sorted before coking to obtain a fraction having a particle size distribution d in the range 0.5 <d <3 mm, and the sorted mixture for further coking is placed in a coke tank or a coke storage container.

An implementation option 20: The method according to any of embodiments 14-19, characterized in that the mixture of petroleum coke before or after mixing the auxiliary means is completely or partially crushed in a grinding device to obtain an average particle size of the residue fraction of less than 3 mm

Option exercise 21: The method according to any of embodiments 1-20, characterized in that the total water content of the charge mixture is adjusted by adding liquid water in the range of up to 7-11.5 mass. %, and this mixture for further coking is placed in a coke tank or coke storage container.

An implementation option 22: The method according to any of embodiments 1-21, characterized in that the charge mixture before filling is sealed with a sealing device to the density of the charge mixture in the range of 0.8-1.225 t / m ³ .

An implementation option 23: The method according to any of embodiments 1-21, characterized in that the charge mixture before filling is compacted with a tamper device to a density of the charge mixture in the range of 1.0-1.150 t / m ³ .

Embodiment 24: The method according to any one of Embodiments 1-23, characterized in that prior to heating, a release layer inert to the combustion is applied to the furnace loading surface.

Embodiment 25: The method of Embodiment 24, wherein said combustion inert separation layer consists of coke.

Embodiment 26: The method of Embodiment 24, wherein said combustion inert separation layer consists of coal.

Embodiment 27: The method of Embodiment 24, wherein said combustion inert separation layer consists of carbon-containing pieces having a grain size of less than 25 mm.

Embodiment 28: The method of Embodiment 24, wherein said combustion inert separation layer consists of ash or sand.

Option exercise 29: The method according to any one of embodiments 24-28, characterized in that the thickness of the separation layer is 0.2-25 cm

Option exercise 30: The method according to any of embodiments 24-29, characterized in that the separation layer is applied to the compacted coke using a machine for sealing coke containing an additional hole designed for this purpose, on the top pusher or top plate.

Option exercise 31: The method according to any of embodiments 24-30, characterized in that the auxiliary agent is stored in a coke tank in a special shaft, from which, when loading, the auxiliary agent is placed in an opening designed for this purpose in a coke sealing machine .

Embodiment 32: The method of Embodiment 31, wherein the auxiliary agent is added to an opening provided for this purpose in the coke compacting machine using a screw conveyor.

Embodiment 33: The method of Embodiment 31, wherein the adjuvant is added to an opening provided for this purpose in the coke compacting machine using a slide system.

Embodiment 34: The method of Embodiment 31, wherein the auxiliary agent is added to an opening provided for this purpose in the coke compacting machine using a chain conveyor system.

An implementation option 35: The method according to any of embodiments 24-34, characterized in that the charge mixture is mixed with auxiliary means in a series of mixing bins of up to four, in which multi-stage grinding and mixing of the crushed material.

An implementation option 36: The method according to any of embodiments 1-35, characterized in that the temperature of the charge mixture before it is loaded into the coke oven is preheated to 120-250 ° C in a heated container.

Embodiment 37: Coke oven for producing coke from petroleum coke obtained from a crude oil refining industry, the furnace

- designed according to the principle of a battery of coke ovens "with heat recovery", has a chamber width in the range of 2-6 meters and a chamber length in the range of 10-20 m, so that at a height of 2 m the volume of the coke oven chamber is 40-240 m ³ , and

- the coke oven has a brick lined apex, which, together with the coke oven chamber below, can form a gas space present above the coke cake in the filled state as the primary heating space, and

- the coke oven is equipped with side channels of the exhaust gases and the secondary heating space below, and

- the coke oven chamber is equipped with a coke storage bin or coke storage container and a loading machine that can load the coke oven chamber from the coke storage bin or coke storage container,

characterized in that

- the coke oven chamber is heated by external burners heating the primary heating space, and the heating gas and oxygen-containing gas are supplied through a collection pipe along the front of the coke oven chamber and adjustable branches to the burners, and

- the burner or burners are located on at least one side of the coke oven chamber, in the wall containing the coke oven chamber door, above the coke oven chamber door, and they heat the primary heating space through an opening located in the wall containing the coke oven chamber door, In this case, a vertical distance of more than 100 mm is established between the outlet of the burner pipe and the upper edge of the portion.

Embodiment 38: A coke oven according to Embodiment 37, wherein the outlet of the burner tube is made of heat resistant steel.

Embodiment 39: A coke oven according to Embodiment 37, wherein the outlet of the burner tube is made of refractory ceramic material.

Embodiment 40: A coke oven according to any one of embodiments 37-39, wherein the coke oven is connected to several additional coke ovens to form a coke oven battery, and a collection pipe extends along the front of the coke oven chambers of the coke oven battery.

Embodiment 41: A coke oven according to any one of embodiments 37-40, wherein the secondary heating space is also heated by an external burner, into which a heating gas and oxygen-containing gas are supplied via a collection pipe along the front of the coke oven chamber, said pipe being open torch on an adjustable branch.

Embodiment 42: A coke oven according to any one of embodiments 37-41, wherein the burner or burners are in the form of burners with fans.

An implementation option 43: Coke oven according to any one of embodiments 37-42, characterized in that the collection pipe is located on the roof of the chamber of the coke oven.

An implementation option 44: Coke oven according to any one of embodiments 37-43, characterized in that the collection pipe is located below the platform for the machine for serving coke ovens.

Embodiment 45: A coke oven according to any one of Embodiments 37-44, wherein the branch or branches are controlled by a faucet, slider, shutter, nozzle, or gate valve.

Embodiment 46: A coke oven according to any one of embodiments 37-44, wherein the coke oven battery comprises a pressure control station in which the heating gas is compressed to the desired pressure and in this state passes from the pressure control station through a collection line to the burners.

Claims (28)

1. Method for the production of blast furnace coke from petroleum coke obtained from a crude oil refining industry, in which • petroleum coke from petrochemical processes is analyzed for volatile matter and ash content so that it can be sorted into portions with a known volatile content and ash content, and • sorting gives a portion of petroleum coke with a volatile content of 15-19 wt.% And an ash fraction of less than 2 wt.% In terms of a portion of petroleum coke that does not contain water and ash, and place it in a coke tank or storage container coke, and • this fraction of petroleum coke from the coke storage tank or coke storage container is placed by loading machines first into sealing means for compaction, and then into a coke oven of a “non-regenerative” design or a “heat recovery” design for cyclic coking, characterized in that • the coke oven is equipped with at least one burner with external heating for heating the primary heating space above the petroleum coke cake or for heating the secondary heating space below the coke oven chamber or both, by means of which the petroleum coke in the coke oven chamber is heated with heating gas to a temperature of 1000-1550 ° C for a period of time less than 120 hours to obtain blast furnace coke having a strength index of CSR of at least 44% and a reactivity index of CRI of less than 33%. 2. The method according to p. 1, characterized in that the volatile content of petroleum coke before coking is 16-18 wt.%. 3. The method according to any one of paragraphs. 1 and 2, characterized in that the heating is carried out in a coke oven with a flame of a burner, which is introduced into the gas space above a portion of petroleum coke. 4. The method according to p. 1, characterized in that the coke oven is equipped with at least one burner with external heating to heat the secondary heating space below the petroleum coke cake, whereby the petroleum coke cake is heated. 5. The method according to p. 1, characterized in that natural gas is used as the heating gas for heating. 6. The method according to p. 1, characterized in that the petroleum coke is ground, and before the specified grinding, petroleum coke is mixed with bituminous coal as an aid, so that the volatile content is in the range of 19-25 wt.% In terms of the dry charge mixture . 7. The method according to p. 1, characterized in that the ash is mixed with petroleum coke as an auxiliary means to set the ash fraction in the range of 2-12 wt.% In terms of the dry total mixture, and this mixture is crushed and sorted before coking, receiving a fraction having a particle size distribution d in the range 0.5 <d <3 mm, and the sorted mixture for further coking is placed in a coke tank or coke storage container. 8. The method according to any one of paragraphs. 6 and 7, characterized in that the petroleum coke before or after mixing the auxiliary means is completely or partially crushed in a grinding device to obtain an average particle size of the residue fraction of less than 3 mm 9. The method according to p. 1, characterized in that the total water content of the charge mixture is adjusted by adding liquid water in the range up to 7-11.5 wt.%, And this mixture is placed in a coke tank or storage container for further coking coke. 10. The method according to p. 1, characterized in that before starting heating, a release layer inert to combustion is applied to the furnace loading surface. 11. The method according to p. 1, characterized in that the temperature of the charge mixture before it is loaded into a coke oven is previously adjusted to 120-250 ° C in a heated container. 12. A coke oven for producing coke from petroleum coke obtained from a crude oil refining industry, the furnace • designed according to the principle of a coke oven battery “with heat recovery”, has a coke oven chamber width in the range of 2-6 meters and a coke oven chamber length in the range of 10–20 m, so at a height of 2 m the volume of the coke oven chamber is 40–240 m ³ and • the coke oven has a brick-faced apex of the roof, which, together with the coke oven chamber below, can form a gas space present above the coke cake in the filled state as the primary heating space, and • the coke oven is equipped with side channels of the exhaust gases and the secondary heating space below, and • the coke oven chamber is equipped with a coke storage bin or coke storage container and a loading machine that can load the coke oven chamber from the coke storage bin or coke storage container, characterized in that • the coke oven chamber is heated by external burners heating the primary heating space, and the heating gas and oxygen-containing gas are supplied through a collection pipe along the front of the coke oven chamber and adjustable branches to the burners, and • the burner or burners are located on at least one side of the coke oven chamber, in the wall containing the coke oven chamber door, above the coke oven chamber door and heat the primary heating space through an opening located in the wall containing the coke oven chamber door. 13. A coke oven according to claim 12, characterized in that the secondary heating space is also heated by an external burner, into which a heating gas and oxygen-containing gas are supplied via a collection pipe along the front of the coke oven chamber, said pipe being opened into the burner by an adjustable branch. 14. Coke oven according to claim 12 or 13, characterized in that the burner or burners are made in the form of burners with fans. 15. Coke oven according to claim 12, characterized in that the collection pipe is located below the platform for the machine for servicing coke ovens. 16. The coke oven according to claim 12, characterized in that the coke oven battery comprises a pressure control station in which the heating gas is compressed to the desired pressure and in this state passes from the pressure control station through a collection pipe to the burners.