WO2010085168A1

WO2010085168A1 - Method and plant for the preparation and deep conversion of hydrocarbon raw materials

Info

Publication number: WO2010085168A1
Application number: PCT/RU2009/000226
Authority: WO
Inventors: Владимир Андреевич ЗОЛОТУХИН
Original assignee: Zolotukhin Vladimir Andreevich
Priority date: 2009-01-21
Filing date: 2009-05-12
Publication date: 2010-07-29
Also published as: RU2387697C1

Abstract

The invention relates to the oil-refining, petrochemical, chemical and fuel-and-energy industries, more specifically, to the preparation and deep conversion of oil, including heavy oil, natural bitumen, residues of oil-refining and petrochemical processes, coal, shale, vegetable products and other liquid, solid and gaseous hydrocarbon media, hereinafter referred to raw materials. The invention can be used for producing hydrocarbon fuel and petrochemical and chemical products. Moreover, the use of said method makes it possible to solve numerous ecological problems and improves environmental situation. The technical result of enhancing the yield of light target products, increasing the depth of raw material processing, simplifying the process and facilities and reducing the cost thereof with a high conversion rate and saving and rationally using hydrocarbon raw material resources, which technical result can be achieved by such a deep conversion process in which the raw materials and a catalyst are not brought into contact, the catalyst is not intoxicated with harmful impurities and is not carbonized, thereby increasing the service life of the catalyst without the need for regeneration processes; furthermore, the conversion rate of 100% can be practically achieved according to the present method by the reiterated, possibly repeated, processing of raw materials and/or the total heavy conversion fraction of the reaction products. The plant is easy to operate and does not require heavy investment and operating costs.

Description

Method and installation for the preparation and deep processing of hydrocarbons

The invention relates to the refining, petrochemical and chemical industries, as well as to the fuel and energy industry, and specifically to the field of preparation and deep processing of oil, including heavy, natural bitumen, residues of oil refining and petrochemical industries, coal, oil shale, vegetable products and other hydrocarbon media, solid, liquid, gaseous, hereinafter raw materials, and can be used in the production of hydrocarbon fuels, petrochemical and chemical products. In addition, the application of the method allows to solve many environmental problems and leads to an improvement in the environmental situation. The preparation and deep processing of oil, oil residues and other raw materials for processing refers not only to the removal of harmful impurities from raw materials, but, most importantly, an increase in the number of light target products higher than their potential content in the feedstock, which allows to significantly increase the processing depth in the future and profitability of the entire processing industry. Light target products or fractions are understood to mean fractions for obtaining light target commercial products with a boiling point mainly up to 350-360 ⁰ C, containing fuel, i.e. the most expensive gas, gasoline, kerosene and diesel fractions, as well as products for petrochemical industries. In the future, light target fractions or products from which, during final processing, are obtained light target commercial products (liquefied gas, tested gasoline, diesel fuel, petrochemicals and other light products). Heavy commercial products - coke, bitumen, bitumen emulsions, coatings, oils and other heavy commercial products.

Currently, the general trend in the oil industry is a decrease in proven reserves of light oil, almost all of the increase in reserves is due to heavy viscous sulphurous oil. Reserves of high-quality raw materials at exploited fields are decreasing, and the share of heavy oil production is increasing. Coals, shales and other solid hydrocarbons are not used on a large industrial scale for the production of motor fuels and petrochemicals.

Processing heavy viscous sulphurous oil is very difficult, energy-intensive and, as a result, is unprofitable or unprofitable. It contains a low amount of "light" (fuel) fractions. In plants with a classical scheme, the selection of these fractions with respect to oil is not more than 25-30%. The high content of sulfur, chlorides and resinous substances reduces the life of the equipment of oil refineries. It’s even more difficult to process oil residues, i.e. residues of oil refining and petrochemical industries, for example, still bottoms after atmospheric or vacuum distillation. There are practically no light products in them, and there are even more harmful impurities than in the feedstock.

In addition, the trend of converting plant products into gasoline and diesel fuel has recently intensified. This is a fundamentally wrong position, which can lead to serious social and environmental consequences on a global scale. It is much more promising to make efforts to increase (up to 100 %) the depth of processing of classical raw materials for these purposes - oil and oil residues, solid and gaseous hydrocarbons, for which the proposed application for the invention is directed.

The issue of deepening refining is the task of the entire world oil refining industry in the near future.

Thus, the preparation of heavy oil for refining, which can include not only the removal of harmful impurities from raw materials, but also an increase in the number of light target fractions above their potential content in the feedstock, is the process that determines the profitability of the entire oil refining industry.

Known and widely used in industry are such methods and schemes for preparing the feedstock as degassing, dehydration and desalting of oil, purification from sulfur, hydrogen sulfide and other harmful impurities (Erich BH, Rasina MG, Rudin MG "Chemistry and technology oil and gas ". Leningrad," Chemistry ", 1972. Skoblo A.I., Tregubova I.A., Egorov N.N." Processes and devices, oil refining and petrochemical industries. Moscow, State Scientific and Technical Publishing House, 1962. A. Dekhterman. Oil refining according to the fuel variant. M., "Chemistry", 1988.).

However, using these methods, only the raw materials are cleaned from harmful impurities, and the fractional composition of the raw materials does not change, therefore, these processes are clearly not enough for cost-effective processing of heavy raw materials (oil, various oil residues), processes are necessary that allow for increased processing amount of light products. In addition, there is still no way to clean the source, especially heavy raw materials, for example, heavy oil or fuel oil, from sulfur and sulfur compounds. Using the famous hydrotreating process purify previously isolated gasoline, kerosene and diesel fuel, but not heavy raw materials.

A known method of thermal cracking for advanced processing of raw materials (Benson S, Thermochemical kinetics, trans. From English., Under the editorship of NS Enikolopyan, M., Mir, 1971 Krasyukov AF, Oil coke, M., Chemistry. 1966. Lukyanov P.I., Basistov A.G. Petroleum pyrolysis. M. Gostoptekhizdat. 1962 Dekhterman A.Sh., Oil refining according to the fuel version, M., Chemistry, 1988). The essence of conventional thermal cracking is that, under the influence of temperature, the vibrational levels of molecules are excited and, when critical energy is reached, bonds break and two more lighter molecules are formed from a more likely heavy molecule. There are a lot of gases and unsaturated hydrocarbons in thermal cracking products, which increases the requirements for further equipment in obtaining marketable products - gasoline, diesel fuel and others. The poor quality of thermal cracking products leads to an increase in capital and operating costs. Therefore, recently, thermal cracking processes, especially in the fuel version, are rarely used. High temperatures of heating of raw materials (470-550 ⁰ C and above) and pressure (up to 7 MPa) also lead to high capital costs, and coking of equipment and low overhaul mileage of equipment - to increase operating costs and the complexity of process control. The operation of thermal cracking units is characterized by a short overhaul time, sometimes no more than 20 days (Dekhterman A.Sh. Oil refining according to the fuel version, M., Chemistry, 1988, p. 51.). Therefore, thermal cracking is not used in world practice as widely as catalytic processes. Also using thermal cracking is not possible to achieve 100% processing depth, because heavy residues such as coke will always remain.

Known methods for processing heavy oil-containing fractions using, simultaneously with thermal, and wave, including cavitation, effects of various nature and a wide range of frequencies, which can be defined as methods of thermomechanical (thermoacoustic, thermowave, i.e. non-catalytic) exposure or cracking .

A known method of processing by sequential extraction of fractions from hydrocarbons using electromagnetic energy with a frequency of 300 MHz-300 GHz (US patent 5055180, class 10 G 1/00, 1991).

In the known method of processing fuel oil by vacuum distillation to obtain distillate fractions, the liquid phase of the still bottom is exposed to acoustic vibrations with a frequency of 0.1-200 kHz and a power of 0.2-3 W / cm ² (USSR author's certificate 1377281, class C lO G 7 / 06, 1988).

There is also known a method of cracking petroleum products using an ultrasonic frequency spectrum. According to this method, the raw material (oil-containing product) and dispersant are fed into the zone, treatment, ultrasonic treatment is carried out with a radiation intensity of 1-10 MW / m ² in a closed circulation circuit at a static pressure in the range from 0.2 to 5 MPa (RF patent 2078116, C 10 G 15/00, 1995).

However, these methods have so far been implemented only in the laboratory version and have not been applied in the industry. But even in the laboratory version, there is no need to talk about a 100% increase in the yield of light target fractions; heavy residues like fuel oil, coke and others. In addition, if, when raw materials are activated by direct heating, heat is directly used to excite vibrational levels of molecules, and to activate the same molecules by wave action, it is first necessary to spend heat (energy) to create a wave effect, and this process has a very low efficiency , then the energy costs when implementing these methods are quite high. But with the proper organization of thermomechanical cracking, provided that energy costs are reduced and optimized, thermomechanical cracking has a good prospect for advanced hydrocarbon processing, since the process is not avalanche-like (as in thermal cracking), but controlled and heavy raw materials do not poison the catalysts due to their absence (RU, patent JNb 74916, 2007).

The most famous and widely used processes of deep processing are catalytic - catalytic cracking, hydrocracking (Sukhanov V.P. Catalytic processes in oil refining. M., "Chemistry", 1973. Prokopyuk C.G., Masagutov R.M. Industrial catalytic cracking units . M., "Chemistry",. 1974.). The essence of catalytic cracking is that bond breaking occurs in the presence of a catalyst, at a high temperature (450-550 ⁰ C and above) and pressure (up to 15 MPa), which lead to a serious increase in capital costs, in hydrocracking - in a hydrogen environment. Catalytic cracking and hydrocracking in various versions (with a stationary catalyst, with a fluidized catalyst bed, with various types of catalysts) are widely used in the world, one of the drawbacks is the very high cost of the process (equipment, catalysts, catalyst regeneration process). In catalytic cracking processes, raw materials and during hydrocracking, the feed and hydrogen are heated and sent to the reactor with the catalyst, then the reaction products are sent to the rectification and preparation of commercial products. Thus, the feedstock is in direct contact with the catalyst in the reactor, hence the main drawback of these processes is the poisoning of the catalyst with harmful impurities contained in the feedstock and the coking of the catalyst surface with heavy reaction products. This leads to the fact that in order to maintain the operability of the processing complex, it is necessary to use processes and equipment for the regeneration or replacement of the spent catalyst, which ultimately leads to a significant complication and cost of process equipment, current and capital costs, and complexity of the process. In addition, heavy residues such as tar, coke, i.e. There is no need to talk about 100% processing depth.

Despite the fact that at present the catalytic processes of advanced processing are the most widespread, even they cannot offer a sufficiently attractive technical and economic balance for many oil refiners when processing the most difficult types of raw materials.

Here you can see that with the help of well-known catalytic technologies it is impossible in principle to solve the problem of 100% processing depth, because heavy oil residues will very quickly lead to coking of the active surface of any catalyst.

The closest analogue is thermal and / or thermomechanical cracking (non-catalytic cracking of raw materials occurs in the absence of catalysts). The aim of the invention is to increase the yield of light target products or fractions (gas, gasoline, kerosene and diesel, as well as products or fractions for petrochemical industries) and, accordingly, increasing the depth of processing, purification of raw materials from sulfur and other harmful impurities, preventing coking and poisoning of the catalyst the process of raw materials and its impurities, simplicity and reliability of equipment design and process control and regulation, process continuity, improving the quality of raw materials and fractions obtained for them further transportation and processing, solving environmental problems, as well as saving and optimal and rational use of hydrocarbon raw materials in their further processing and obtaining targeted marketable products. The main goal is to increase the depth of processing of any hydrocarbon feedstock, which ultimately leads to an increase in the profitability of the entire processing industry. Because the catalyst is not poisoned by raw materials during cracking and its replacement or regeneration is not required, this should lead to a reduction in operating and capital costs.

The technical result, the proposed method is aimed at, and the goal is achieved by such an organization of the preparation process and deep processing, in which the raw materials and the catalyst do not contact, as a result of which the catalyst is practically not poisoned by harmful impurities and does not coke, which leads to an increase in the durability of the catalyst and the absence of the need for regeneration processes. To achieve a high processing depth, the raw material is subjected to the process of preparation or processing of this method repeatedly. Liquid (e.g., oil, fuel oil, oil refining and petrochemical residues) feedstocks are heated or heated and subjected to thermal and / or thermomechanical cracking without catalysts and reagents (you can also use any other types of cracking - with the help of electromagnetic or radioactive radiation and other similar processes), molecular hydrogen or light hydrogen-containing media enriched with hydrogen, for example, associated gas, natural gas, including gas obtained during the preparation and deep processing, pentane fractions, xylene, toluene, part of the light shoulder straps of gasoline and other light fractions, including those obtained during the preparation and deep processing of this method, if necessary osti (especially if the hydrogen-containing raw material is a liquid and must be transferred to the vapor-gas phase) are heated separately from the raw material, sent at a higher pressure than the pressure in the heating and / or cracking stage, to the stage of production of active atomic hydrogen and / or light radicals in a reactor with a catalyst heated to the required temperature (approximately 300 - 500 ⁰ C and more), after which active hydrogen and / or light radicals are sent to the heating and / or cracking zone of the feedstock for the reaction, the reaction products are sent to stage p obtaining commercial products or to the separation stage in which the reaction is completed, the light target reaction fractions, mainly with a boiling point up to 350-360 ⁰ C, are sent to the stage of obtaining light target commercial products such as liquefied gas, gasoline, kerosene, diesel fuel, petrochemical products at the place of preparation and deep processing of raw materials by this method or transported to a remote place for the production of light commercial products, the heavy residue after the separation stage, mainly with the pace Aturi initial boiling point of 360 ⁰ C and above, is directed to obtain heavy bitumen commodity type products, coke and other, or partially or completely directed to the stage of purification from harmful impurities, then for reprocessing by this method at the beginning of the process (at the heating stage - to the heater) together with the feedstock or separately to the next stage or treatment unit, solid hydrocarbon raw materials (for example, coal, shale, vegetable products and others) are sent to the stage of fine grinding and introduced into the feedstock and / or a heavy separation residue before it is processed again, gaseous hydrocarbons are also introduced into the feedstock and / or the residue section Before its reprocessing, liquid, solid and gaseous hydrocarbons can be processed by this method simultaneously, individually or in pairs, with the stages of heating and / or cracking of the feedstock and / or the residue of separation, heating of hydrogen or hydrogen-containing media and a catalyst, production of active atomic hydrogen and the separation into the light part and the heavy residue can be combined in one apparatus. Part of the gaseous and / or light products (they are enriched with hydrogen and can replace the original hydrogen-containing medium) separation can be returned to the beginning of the process in a reactor with a catalyst to produce active atomic hydrogen and / or light radicals. In addition, unreacted hydrogen and / or light hydrogen-containing media are isolated from the gaseous and / or light part of the separation, which are returned to the beginning of the process for recycling, which also leads to lower operating costs. Or they return to the beginning of the process along with some of the gaseous and light separation products. Gaseous and light return media must be cleaned from harmful impurities, for example, from hydrogen sulfide, which is formed during the cracking of raw materials, before reuse. Cleaning is carried out by well-known methods (links to methods purification from harmful impurities are given above). In addition, part of the gaseous and / or light fractions can be returned to the beginning of the process and used for reprocessing together with the feedstock, which leads to a change in the fractional and group composition of the obtained fractions and products, for example, to increase the yield of aromatic compounds for further production of petrochemical products . The temperature of 350-360 ⁰ C is currently the boundary temperature between light and heavy target products, however, over time, guests and requirements for fractional composition of motor fuels and petrochemical products may change and the boundary temperature may change in any direction. According to this method, the changing requirements are easily satisfied by changing the process temperature accordingly at the separation stage. To ensure the completeness of saturation reactions of open radical bonds obtained in the process of cracking the feed, the number of hydrogen atoms and / or light radicals obtained in the reactor with the catalyst should exceed the number of open bonds of the cracking radicals of the feed and the ratio of the surface of the reactor to the catalyst (stage of production of atomic hydrogen and / or light radicals) to the volume of the heating and / or cracking zone of the feedstock is maximized so that the active hydrogen and / or light radicals most fully react with the cracked m raw materials. When reprocessing, the heavy residue is optimally heated separately from the raw material (in different furnaces or heaters, or in the same furnace, but in different coils), especially if the raw material is light. In this case, the speed of movement of raw materials and heavy residue in the coils should be higher than 1 m / s (optimally in the range of 3 ÷ 10 m / s) to reduce coking of the coils. To implement the above methods apply standard well-known installation. Installation for cracking petroleum products contains a device for processing raw materials, in communication with a device for separation, fractionation of final products, communicated, in turn, with a device for obtaining and cooling the final product (for example, gasoline). A device for processing raw materials by a catalytic method is a capacitive apparatus with either a dense or moving bed of a large-spherical cracking catalyst organized inside it, or with a fluidized bed of a microspherical cracking catalyst ^ in ^* which contacts the processed raw material in the vapor phase with the catalyst and the reaction of the splitting of hydrocarbon molecules . A device for thermal processing of raw materials is a capacitive apparatus or a coil in which the raw material is heated above the temperature of thermal cracking. A device for processing raw materials by the thermomechanical method is an apparatus in which the cracking of raw materials is carried out by means of joint heat treatment and wave processing of various nature and a wide range of frequencies. The device for fractionation of final oil products is a column apparatus with a cascade of separation plates organized inside. A device for cooling and condensation is a heat exchanger of any design, for example, shell-and-tube. The separation device is a capacitive apparatus, part of the internal volume of which is filled with a separation mixture. In the upper part of the device there is a pipe for venting gases, in the bottom for venting liquid. In addition, the plants are equipped with tanks for feedstock and commercial products, pipelines, control - measuring instruments, automation (Rudin MG Drabkin AE Oil refiner short reference L. Chemistry, 1980, pp. 65-73).

However, these installations and methods have significant disadvantages described above, in addition, with their help it is fundamentally impossible to increase the processing depth to 100%.

This goal is achieved by the fact that gaseous molecular hydrogen and / or light hydrogen-containing fractions enriched with hydrogen, for example, associated or natural gas, or gas from oil refining and petrochemical processes, methane, propane - butane mixtures, pentane fractions, xylene, are in direct contact with the heated catalyst toluene, light shoulder straps of gasoline fractions, including gas and light fractions of the process of the proposed process, used to produce active atomic hydrogen and / or light radicals, which are then react with heated to a certain temperature and / or cracked raw materials. Hydrogen-containing fractions and / or the catalyst must be heated, because the detachment reaction of a hydrogen atom is endothermic and requires energy. Molecular hydrogen or light hydrogen-containing products do not contain asphaltenes, carbenes, gummy and coke-like substances, as well as harmful impurities, and their interaction with the catalyst does not lead to its coking and poisoning. As hydrogen-containing fractions for the generation of atomic hydrogen, not only hydrocarbons can be used, but also other substances enriched with hydrogen, for example, water and / or water vapor. Heavy raw materials do not come into direct contact with the catalyst, poisoning and coking do not occur, there is no need for catalyst regeneration, the process is simplified and becomes more reliable, the cost of the process and equipment is significantly reduced, i.e. capital and operating costs, the processing depth can be increased to almost 100%. In this case, there is a saving of raw materials in the development of the required number of target commodity products, in other words, the optimal and rational use of raw materials during their further processing when implementing this method. In addition, various residues and wastes that accumulate in the process, for example, oil production and refining, lead to environmental degradation, and their processing by this method with the production of highly liquid products allows solving environmental problems, as well as making additional profit /

Raw materials are heated separately from hydrogen or hydrogen-containing products, but can be heated in the same heating apparatus, for example, in the same fire furnace, but in different coils.

Thermal cracking for heavy oil has features: starting from about 420 ⁰ C or more (depending on the raw material), thermal cracking proceeds at a high speed, i.e. on an industrial scale. (Soskind D.M., Ratov A.N. Small-tonnage complex for oil refining in the Ulyanovsk Region with associated vanadium recovery. "Chemistry and Technology of Fuels and Oils", N ° l, 1996). The heating temperature of the raw material is selected from the requirements for the resulting final products. The higher the temperature, the more gases and unsaturated hydrocarbons are formed. In thermomechanical cracking, the feed is heated thermally, i.e. the most economical method in this case, up to a certain temperature, which is lower than the temperature of the onset of avalanche-like uncontrolled thermal cracking, i.e. heated so that uncontrolled thermal cracking has not yet begun. Heating can be carried out in a fire or electric furnace, or another type of furnace, as well as in various heat exchangers designs in which the raw material is heated with a coolant. Raw materials heated to subcritical temperature (vibrational levels of molecules are already excited, but there is no avalanche-like breaking of molecules due to this excitation) are sent to the processing stage, in which the raw material is subjected to mechanical (e.g., cavitation) and wave action of various natures (sound, ultrasonic, cavitation electromagnetic, light, radiation) and a wide range of resonant frequencies. Then, the raw material treated with thermal or thermomechanical action is reacted with active atomic hydrogen and / or light radicals, the open bonds of the cracking radicals of the feed are saturated, and isomers, aromatic hydrocarbons and other valuable fractions are formed instead of unsaturated hydrocarbons. The reaction products are sent to the stage of obtaining marketable products or first to the stage of separation into light target reaction fractions, mainly with a boiling point up to 350-360 ⁰ C, and a heavy separation residue. The second option is more promising, because Allows you to direct the remainder of the separation in whole or in part to re-treatment at the beginning of the process, which leads to an increase in the depth of processing of raw materials.

When bonds are broken in hydrocarbon molecules, more likely polyatomic, smaller molecules are formed, i.e. more boiling products, but with open unsaturated bonds, i.e. poor quality products. In the future, this can lead either to the formation of unstable reaction products, or to condensation processes, i.e. to the formation of heavy 'molecules. The secondary formation of heavy molecules leads to a decrease in the expected processing depth. Unstable products reactions with open bonds in the future, upon receipt of marketable products or transportation, in contact with air can be attached, for example, oxygen, which leads to the formation of resins. The increased resin content in the fuel leads to increased formation of soot in the engines and their premature failure. Therefore, open communications must be closed, i.e. to saturate with any elements, for this topic - obtaining light target fuel components (gasoline, kerosene, diesel fractions), as well as components for further obtaining petrochemical products - it is necessary to saturate the bonds with hydrogen atoms and / or light radicals, because molecular hydrogen is not very chemically active, and even a hydrogen molecule cannot be attached to one open bond. The quality of the obtained fractions is significantly improved. Instead of unsaturated hydrocarbons, saturated isomers with a large octane number and aromatic hydrocarbons as good raw materials for the production of petrochemical products are obtained.

Atomic hydrogen is much more active than molecular hydrogen. So, atomic hydrogen, under ordinary conditions, combines with sulfur, phosphorus, arsenic, etc., reduces the oxides of many metals, displaces some metals (copper, lead, silver and others) from their salts and enters into other chemical reactions to which Under the same conditions, ordinary molecular hydrogen is not capable. Noticeable thermal dissociation of hydrogen begins at about 2000 ^° C and effectively occurs when the temperature reaches 5000 ° C. Naturally, to saturate the unsaturated bonds of unsaturated hydrocarbons formed during cracking, it is impossible to use thermal dissociation to form atomic hydrogen — too high temperatures are required. In addition to high temperatures There are many other methods for producing active atomic hydrogen and / or light radicals. The rate of reactions of the formation of atomic hydrogen and / or light radicals from molecular hydrogen and light hydrogen-containing media increases with the use of catalysts (platinum group metals, transition or heavy metal oxides, aluminosilicate, zeolite-containing and other types of catalysts), excitation methods using wave action with a wide spectrum of frequencies of various nature and intensity (light, electric discharge, electric arc, radioactive radiation), as well as using chemical reactions. In an atomic form, hydrogen reacts with almost any elements and molecules, except for noble gases (B. Nekrasov, Fundamentals of General Chemistry. M., 1973). As already mentioned, active hydrogen is much more active than molecular hydrogen, and it reacts with almost all substances, including hydrocarbon molecules, and not just radicals. In addition, if the feedstock is heated to a subcritical temperature, at which the vibrational levels of the molecules are in an excited state, but avalanche-like breaking of the bonds (cracking) has not yet occurred, then not only atomic hydrogen, but also light radicals obtained can efficiently react with such molecules in a reactor with a catalyst, which also have a high reactivity. Those. the process of preparation and deep processing of hydrocarbon raw materials can be carried out without cracking the raw materials, however, this process is still poorly studied, but has broad prospects, because can take place at lower temperatures and energy costs than with the implementation of thermal and / or thermomechanical cracking. The coking process of heating equipment is also virtually eliminated. In this case, raw materials, especially heavy ones, must be heated. to a temperature at which the raw material becomes low viscosity and flows well, to a temperature above 20-50 ⁰ C.

The production of atomic hydrogen and / or light radicals using the methods of wave excitation and chemical reactions under industrial conditions of the oil refining complex is not yet the most effective way, although with the further development and optimization of such processes it has a good perspective.

The most real results in industrial conditions can be achieved using catalysts. For this, gaseous molecular hydrogen, hydrogen-containing media and / or a reactor with a catalyst are heated to a temperature of 300-500 ⁰ C, and sometimes even higher (although more effective catalysts can be found over time that will allow the formation of hydrogen and / or light radicals at lower temperatures, for example, at 20-100 ⁰ C and below). The processes of catalytic decomposition of hydrocarbons are widely known, some references are given above. In this case, during the interaction of hydrogen and hydrogen-containing media with molybdenum, cobalt, zinc, vanadium, nickel, aluminosilicate, zeolite-containing and other catalysts, for example, based on aluminum oxide, or other types of catalysts, atomic hydrogen and / or light active radicals of catalytic cracking of hydrogen-containing are formed media that effectively saturate open bonds of light radicals obtained by the reaction of thermal or thermomechanical cracking of hydrocarbon feeds into cut tate formed which light saturated fraction target of good quality. For example, an ethane molecule containing 2 carbon atoms and 6 hydrogen atoms in a reactor with a catalyst (in the process of catalytic cracking of hydrogen-containing fractions) can form 2 light radicals, each of which contains one carbon atom and 3 hydrogen. These light radicals, together with the light cracking radicals of the feed, form a light target product molecule. It also happens with other light hydrogen-containing media. Light radicals obtained by detaching active atomic hydrogen from used hydrogen-containing media also attach to light cracking radicals of the feed, saturate their open bonds and form target fractions. If they (or atomic hydrogen) are attached to the heavy radicals of the cracking of the feed, then after the separation stage the heavy reaction residue is sent either partially or completely to the reprocessing by this method, or partially or fully to obtain heavy commercial products such as coke, bitumen and others ( depending on the task). However, much more light radicals are formed during cracking of raw materials than heavy ones, because most likely, a long raw material molecule breaks in about the middle, and with a much lesser probability is a very small and very large radical. This is evidenced, for example, by thermal cracking processes, as a result of which lighter fractions in larger quantities are obtained from heavy raw materials than heavy ones. Therefore, a significantly smaller amount of separation residue is sent for reprocessing than raw materials. In this case, the separation residue can be sent for re-treatment at the beginning of the process together with the feedstock, or separately for an additional processing stage in this way. The separation residue may be heated together with the raw material or separately, in a separate furnace coil or in a separate heater (furnace). In the latter case, the temperature of the residue can be much higher than the temperature of the raw material, and thermal or thermomechanical cracking Raw materials are produced through interaction, for example direct mixing, with a heated heavy separation residue. If the feedstock is not sufficiently purified, for example, of mechanical impurities, then in the heavy separation residue their concentration increases significantly and it is necessary to clean it before reprocessing the residue. With repeated reprocessing of the heavy separation residue (the entire residue is returned to the beginning for recycling), the feedstock will be processed into light target products with an efficiency of up to 100%.

It is in principle possible to use liquid and / or gaseous catalysts. By mixing them with hydrogen and / or hydrogen-containing media, it is possible to carry out a cracking reaction and produce atomic hydrogen and / or light radicals, which are then introduced into the cracking zone of the feed for the reaction. However, this process has not yet been practically studied.

Hydrogen-containing media and a reactor with a catalyst can be heated to produce atomic hydrogen and / or light radicals using separate heaters of various types, but it is most economical to use the heat of a heated feedstock or separation residue. The temperature of the raw materials for carrying out the reaction of thermal and / or thermomechanical cracking usually exceeds 420 ⁰ C and lies in the temperature range of the use of catalysts for the dissociation of hydrogen. For this purpose, widely known heat exchangers of various types and designs are used.

In addition to increasing the depth of processing during the implementation of the proposed method, the feedstock is purified from sulfur and other impurities. The energies of the carbon - heteroatom bonds (carbon - sulfur ,, carbon - nitrogen and others) are lower than the carbon - carbon and carbon - hydrogen bonds (T. V. Bukharkina, H. G. Digurov. Natural Chemistry energy and carbon materials. M., 1998). Therefore, for example, sulfur atoms, the purification of the feedstock from which is problematic, are more likely to disconnect from the hydrocarbon molecule during cracking, and when this method is implemented, they form hydrogen sulfide. Hydrogen sulfide is easily released in a gaseous form and disposed of to produce atomic sulfur or other sulfur-containing commercial products.

The light target reaction fractions after the separation stage, mainly with a boiling point up to 350-360 ⁰ C, which are mainly in gas-vapor and droplet form, contain gas, gasoline, kerosene and diesel fractions, as well as fractions for producing petrochemical products. The gas fractions are purified, for example, of hydrogen sulfide, then sent to obtain marketable products, such as liquefied gas, or used as fuel for their own needs on the spot. In addition, the gas separation part is a hydrogen-enriched light product, and can be partially or fully used at the stage of producing atomic hydrogen and / or light radicals together with molecular hydrogen or light hydrogen-containing fractions enriched with hydrogen coming from outside the process. For the same purpose, the lightest part of the obtained gasoline fractions obtained in the process of preparation and deep processing of raw materials by this method can be used. For this, the light part after the separation stage, but before the stage of obtaining light commercial products, is sent to the stage of separation of the gas part and the lightest fractions, after which they are sent to the reactor with a catalyst to obtain active atomic hydrogen and / or light radicals. This can be done using degassers of various designs or protozoa. distillation columns. This leads to a partial saving of molecular hydrogen and hydrogen-containing fractions coming from outside the process. Together with gas and light separation fractions, hydrogen and / or hydrogen-containing media that did not manage to react with the feedstock return to the beginning of the process, which leads to a reduction in operating costs. The remaining target fractions are sent to the stage of obtaining the target marketable products such as gasoline, kerosene, diesel fuel, petrochemical products at the place of preparation and advanced processing of raw materials by this method or, after cooling and condensation, are transported to a remote place of receipt of light marketable products. At the same time, such expensive processes as hydrotreating, reforming, and other well-known processes in the units for obtaining light commercial products may not be used, because open bonds of the cracking radicals of the raw material are saturated to the unit for obtaining marketable products, and the properties and composition of the obtained fractions are adjusted by changing the mode and process parameters.

If the production of molecular hydrogen is currently a rather expensive process, the use of natural or associated gas, which in many cases is flared, for the production of atomic hydrogen and / or light radicals, minimizes the cost of the downstream process.

The proposed method can be used for the preparation and deep processing of solid and gaseous hydrocarbons.

Solid hydrocarbon feedstocks (e.g. coal, shale, vegetable products) are preliminarily crushed into a fine powder and introduced into a liquid feedstock and / or into the separation residue before it is processed again by this method (mixed with raw materials and / or separation residue). For solid hydrocarbons, the liquid feed or residue in this case is heat and carrier. In this case, under the influence of temperatures and in the presence of active atomic hydrogen, hydrocarbon molecules of various sizes are formed. Light hydrocarbons will be separated out at the separation stage and used to produce light target commercial products, heavy hydrocarbons will be returned for reprocessing and, when processed in this way several times, solid hydrocarbon raw materials with an efficiency of up to 100% will be processed into target fractions and products. The prospects for this approach to the preparation and deep processing of solid hydrocarbons are obvious, because reserves of, for example, coal exceed oil reserves by hundreds of times, however, oil is used for the production of fuel products, because so far there are no satisfactory coal processing technologies for these purposes. Because solid hydrocarbons contain harmful impurities, mainly inorganic, the separation residue must be cleaned from them before re-processing.

The situation with the processing of gaseous hydrocarbons is much better, but even here all the problems have not been resolved. For example, during oil production, a huge amount of associated gas is burned, while enormous environmental damage is caused and valuable hydrocarbon raw materials are destroyed. This method allows you to effectively use such hydrocarbons, mixing them into the original liquid raw materials and / or heavy separation residue during its reprocessing by this method (similar to the preparation and deep processing of solid hydrocarbon raw materials in the form of a fine powder for further in-depth processing), or use as hydrogen-containing products in the production of atomic hydrogen. Such low-cost complexes can be used at the site of oil production to improve the quality and cost of raw materials before transportation.

In addition, gaseous hydrocarbons can be used as an independent feedstock for the preparation and deep processing similar to liquid feedstock. In this case, gaseous hydrocarbons can be used as heat and a carrier in the processing of solid hydrocarbons in the form of fine powders, as well as for the processing of liquid hydrocarbons introduced, for example, in the form of small drops.

Depending on the task, this method can be used to process liquid, solid, gaseous raw materials at the same time, or in pairs, or separately liquid or gaseous hydrocarbons.

The problem was also solved by creating a plant for the preparation and deep processing of hydrocarbon feeds, in which the device for processing and cracking of feedstock further comprises a reactor with a catalyst for producing active atomic hydrogen and / or light radicals from molecular hydrogen or light hydrogen-containing media enriched with hydrogen, for example , natural or associated gas, gas and light fractions of oil refining and petrochemicals, in particular gas and light fractions obtained in the preparation and deep processing by this method. If necessary, the reactor for producing atomic hydrogen and / or light radicals is equipped with devices for heating hydrogen-containing media and a catalyst, and the pressure in the reactor with the catalyst is greater than the pressure in the device for heating, processing and cracking of raw materials, the reactor with the catalyst is made in the form of a cylinder, a ball , an annular cylinder, parallelepiped or other three-dimensional figure, for example, in the form of a tubular coil, with a catalyst in the form of granules placed in it of arbitrary size and shape, the surface of the reactor with the catalyst is permeable to atomic hydrogen and / or light radicals, for example, made of a porous material, or holes of arbitrary shape are made on the surface of the reactor, the holes being smaller than the size of the catalyst granules, and in the heating device / or cracking can accommodate more than one reactor with a catalyst, i.e. a package of reactors, or several packages of reactors, moreover, a reactor with a catalyst or packages of reactors can be located either along the movement of the feed stream, or across or in an intermediate position. The reactor with the catalyst may not contain granules or powder of the catalyst, while the shell of the reactor or the entire reactor is made entirely of material that is a catalyst for carrying out the process of producing atomic hydrogen and / or light radicals from molecular hydrogen and / or hydrogen-containing media. The catalyst body has a collector for distributing hydrogen and / or hydrogen-containing media. The number of hydrogen atoms and / or light radicals produced in the reactor with the catalyst must exceed the number of open bonds of the cracking radicals of the feedstock, and the ratio of the surface of the reactor with the catalyst to the volume of the heating and / or cracking zone is increased so as to maximize the reaction of the feedstock and atomic hydrogen and / or light radicals.

In addition, a collector can be installed inside the reactor with the catalyst for uniform distribution of molecular hydrogen or hydrogen-containing fractions over the cross section and volume of the reactor.

Holes of various sizes can be made on the surface of the reactor with the catalyst so that active hydrogen and / or light radicals fall into the reaction zone with the feed, or a reactor with a catalyst is made of a porous material with different pore sizes, for example, in the nanometer range.

The reacted products can be fed to devices for obtaining the target end products, bypassing the separation stage (the scheme is obvious, therefore, is not given in the description). But in order to achieve a processing depth of almost 100%, it is necessary to supplement the installation with a separation device, in which the reaction is completed, light target reaction fractions after the separation device, mainly with a boiling point of up to 350-360 ⁰ C, are sent to the device for obtaining the target marketable products of the liquefied type gas, gasoline, kerosene, diesel fuel, petrochemicals at the place of preparation and advanced processing of raw materials, by this method, or transported to a remote place to receive light t ovarian products, or part of them together with d, with unreacted hydrogen and / or hydrogen-containing media are sent to the beginning of the process to produce atomic hydrogen and / or light radicals. The heavy residue after the separation device, mainly with a boiling point of 360 ⁰ C and above, is partially or completely sent to produce heavy commercial products such as bitumen, coke, and / or partially or completely sent for re-processing according to this method to the beginning of the process together with the original raw materials or separately to the next stage of processing. The separation device may be an atmospheric distillation column, or a capacitive apparatus, the lower part of the internal volume of which is filled with the heavy part of the separation. In the upper part of the device there is a pipe for the removal of gases and vapors, in the lower for the removal of liquid. For an effective process of separating the liquid phase from the vapor-gas, usually reacted raw materials dispersed (sprayed) with decreasing pressure into a separation device to increase the interface.

The most economical devices for heating and / or cracking raw materials and / or the separation residue, heating hydrogen or hydrogen-containing media and a catalyst, producing active atomic hydrogen and / or light radicals and separating into the light part and heavy residue combine in one apparatus, and heating of hydrogen or hydrogen-containing media and catalyst to implement due to the heat of the heated raw materials and / or separation residue.

Atomic active hydrogen and / or light radicals can be obtained using radioactive radiation, wave action on hydrogen and hydrogen-containing media with a wide range of frequencies of various nature and intensity, as well as using chemical reactions, but so far the application of such methods in industrial conditions is not as effective as using catalysts.

For processing solid hydrocarbon feedstock, the installation further comprises a device for finely dispersing the solid hydrocarbon feedstock, which is introduced into the feedstock and / or separation residue. The gaseous feed is simply introduced into the liquid feed and / or separation residue.

Because solid hydrocarbon raw materials contain many impurities, inorganic in particular, the installation additionally contains a device for purification of harmful impurities and compounds of the separation residue before its reprocessing.

In general, an industrial step-by-step implementation scheme of the proposed method is shown in FIG. 1, 2, on which is indicated: 1 - stage of heating of raw materials and heavy separation residue (heater); 2 - cracking stage; 3 - stage heating of hydrogen or hydrogen-containing environments; 4 - stage for the production of atomic hydrogen and / or light radicals (reactor with a catalyst); 5 - separation stage (at the separation stage, an atmospheric distillation column can be used in which the products supplied to it are separated into a gas part, several light fractions and still bottoms); 6 - stage of preparation of light target commercial products (gasoline, kerosene, diesel fuel, petrochemicals); 7 - stage of preparation of heavy commercial products (bitumen, bitumen emulsions, coatings, coke); 8 - stage finely divided grinding of solid hydrocarbon feedstocks. The stage of preliminary purification of raw materials (degassing, dehydration, desalination, purification from mechanical and other harmful impurities) is not shown in the figures for simplicity. Also, for simplicity, the elements of the necessary infrastructure are not shown - a commodity and raw materials park, flyovers, etc. The stages of obtaining marketable products usually include the following well-known processes: hydrotreating, reforming, platforming and other processes of the petrochemical and chemical industries, or at the first stage.; compounding stages, a bitumen block for the production of oxidized bitumen or a bitumen block combined with a vacuum block for the production of non-oxidized bitumen, as well as equipment for the production of bitumen coatings, emulsions, boiler fuel, coke and other commercial products (Petrochemical Handbook. Two volumes. Volume 1 , under the editorship of Ogorodnikov CK. L., Chemistry, 1978, p. 53-55).

The purified feed (purification step not shown) is fed to the heating step (FIG. 1, position 1), then to the cracking step (FIG. 1, position 2). Hydrogen or light hydrogen-containing media are fed to the heating stage (Fig. 1, position 3), then to the stage of producing atomic hydrogen and / or light radicals (Fig. 1, position 4), the resulting atomic hydrogen and / or light radicals are fed to the cracking stage (Fig. 1, position 2), where it reacts with the cracked feed and saturates open bonds of the cracking radicals of the feed. The reacted feed is fed to the separation step (Fig. 1, position 5), in which it is separated into light target reaction fractions, mainly with a boiling point up to 350-360 ⁰ C, and a heavy residue, mainly with a boiling point of 360 ⁰ C and above. After the separation stage (Fig. 1, position 5), part of the gas and light fractions together with unreacted hydrogen and / or hydrogen-containing media after purification from harmful impurities (purification stage for simplicity not shown), for example, from hydrogen sulfide, is returned to the beginning of the process, the remaining light target fractions are directed to the stage of obtaining the target marketable products (Fig. 1, position 6) such as liquefied gas, gasoline, kerosene, diesel fuel, petrochemical products and others, the heavy residue is partially or completely directed to the floor stage heavy commercial products (Fig. 1, position 7) such as bitumen, coke and others, and / or partially or completely sent for re-processing according to this method to the beginning (to the heater) of the process. The stages of obtaining marketable products can be removed from the place of preparation and deep processing by this method, then light and heavy separation fractions must be transported, after cooling, to the place of production of marketable products. In addition to the processing of gaseous hydrocarbons in addition to liquid raw materials, they are introduced into the feedstock and / or the residue when it is recycled (as well as solid hydrocarbons, it is not shown in the diagram for simplicity). Solid hydrocarbon feed is supplied to the stage of fine grinding (Fig. 1, position 8), then introduced into the original liquid feed and / or the remainder of the separation before reprocessing it. When using solid hydrocarbon feedstocks, it must be taken into account that it contains a lot of impurities, in particular inorganic ones, therefore, before re-processing the separation residue, it must be cleaned (the purification step is not shown in the diagram for simplicity), for example, as well as the raw materials are cleaned of mechanical impurities.

If the entire remainder of the separation, i.e. If all heavy high molecular weight separation fractions are returned for reprocessing at the beginning of the process, then it is advisable to use the oil refining scheme without the stage of obtaining heavy commercial products (Fig. 2). In this case, almost 100% processing of the feedstock is achieved (calculated by the yield of light target fractions or products).

In figures 3 to 15 are sections of the main units of the installation, preparation and deep processing of hydrocarbons.

In FIG. 3 - 15 is indicated (in accordance with the notation in Fig. 1): 1 - a device for heating raw materials; 2 — cracking device (usually a portion of a heated coil); 4 - a device for producing atomic hydrogen and / or light radicals (reactor with a catalyst); 5 - separation device, as one of the options is an atmospheric distillation column; 9 - a collector for the distribution of hydrogen or hydrogen-containing fractions throughout the volume and cross section of the reactor with the catalyst; 10 - surface of a reactor with a catalyst with holes or a permeable surface for the passage of hydrogen or hydrogen-containing fractions, as well as atomic hydrogen and light radicals; 11 is a catalyst, usually poured into the reactor in the form of granules. A longitudinal vertical section through the apparatus is shown in FIG. 3. As a heater (item 1) of the raw materials, electric, induction heaters of various types can be used. In the industrial version most often used fire heating furnaces. The coil portion heated in the firing furnace is shown in FIG. 4. A heater of hydrogen or hydrogen-containing fractions is not shown for simplicity. A raw material cracking device can be a capacitive apparatus, but the most optimal thermal and / or thermomechanical cracking of raw materials can be carried out in a device in the form of a pipe or coil in a heating furnace (Fig. 3, 4, position 2). A device for heating or heating and cracking a feed is supplemented with a device for producing atomic hydrogen and / or light radicals (reactor with a catalyst), FIG. 3, 4, position 4, which in this case is heated due to the temperature of the heated raw material. Simultaneously with heating in order to initiate cracking of the feed, it is advisable to expose the product stream sequentially or simultaneously to cavitational, sound, ultrasonic effects created by the movement of the flow, moreover, a mixture of hydrocarbons can be exposed to this effect repeatedly, and active hydrogen and / or light radicals are supplied to cavitation devices, sound, ultrasonic exposure. Special devices are also used for cavitation oil treatment and application of acoustic impact on it, the action of which is based on the hydrodynamic effects of medium moving at high speed (above 5 m / s) along channels with obstacles of various shapes and different curvatures. The heavy separation residue may be mixed with the feed before reprocessing and heated together, or heated separately from the feed in the same or separate heater. In this case, it can be heated to higher temperatures than raw materials, because in the heavy residue is much less light fractions than in the raw material. In this case, the cracking of the raw material can be carried out due to its interaction with the separation residue heated to a high temperature, for example, direct mixing and further joint movement with high speeds along the channels from obstacles of various shapes and curvatures. Those. in addition, the device for heating and / or thermal cracking of raw materials can be equipped with a device for acoustic, cavitation processing of raw materials (there are many designs of devices, for simplicity, not shown in Figs. 3, 4) for thermomechanical cracking. Processing devices, as well as heating raw materials, can be located both outside the pipeline or capacitive apparatus through which the raw materials flow, and inside it. Flowing through the pipeline, the raw material is heated, or heated and subjected to thermal and / or thermomechanical cracking, while active atomic hydrogen is fed from the reactor with the catalyst into the heating or heating and cracking zone of the raw material (Fig. 3, 4, position 4).

A reactor with a catalyst for producing active atomic hydrogen and / or light radicals can have an arbitrary shape - a cylindrical rod, in the form of an annular cylinder, a parallelepiped, a plate, a ball, a tubular coil, in the form of a volumetric figure of any shape in which the catalyst is placed, for example, in the form pellets of small size, usually up to several millimeters (catalysts with sizes of 50-100 micrometers are also used in catalytic cracking processes). The reactor with the catalyst may not contain granules or powder of the catalyst, while the shell of the reactor or the entire reactor is made entirely of material that is a catalyst for carrying out the process of producing atomic hydrogen and / or light radicals from molecular hydrogen and / or hydrogen-containing media. The catalyst body has a collector for distributing hydrogen and / or hydrogen-containing media. The surface of the reactor with the catalyst should be developed in relation to the zone heating, cracking of raw materials so as to maximize the interaction (reaction) of atomic hydrogen and / or light radicals and heated or cracked raw materials for the efficient use of reactive products. In FIG. 5 is a vertical longitudinal section through a reactor with a cross-collector rod cylinder catalyst; FIG. 6 to 8 show a section through a longitudinal collector reactor. Heated molecular hydrogen or hydrogen-containing fractions are fed into a transverse (Fig. 5, position 9) or longitudinal (Fig. 6 - 8, position 9) collector, from which hydrogen or hydrogen-containing fractions through pores or holes (Fig. 5 - 8, position 10) arbitrary shapes and sizes fall into the volume with the catalyst (Fig. 5 - 8, position 11). This can be a catalyst in the form of granules or powder placed between the surfaces of the collector and the reactor, or in the form of a solid with holes or a porous catalyst of the process, which forms the body and walls of the reactor with the catalyst. The active atomic hydrogen and / or light radicals formed in it, through the corresponding pores or holes on the outer surfaces of the reactor with the catalyst (Figs. 5-8, position 10), enter the reaction zone with the feed. The size of the holes should be smaller than the size of the granules of the catalyst. Because the process of formation of atomic hydrogen and / or light radicals during cracking of hydrogen-containing media is probabilistic and takes some time (in hydrocracking processes up to several seconds), the initial part of the outer surface of the reactor with the catalyst can be closed for the passage of active hydrogen and light radicals, as shown in FIG. 6. The shape of the outer surface of the reactor with the catalyst may have a streamlined shape both at the end of the reactor (Fig. 5, 7) and at the beginning (Fig. 8), i.e. the entire reactor has a smooth surface shape for better flow around raw materials. A promising form for a reactor with a catalyst is one in which the outer surface has the shape of an aerodynamic wing, especially a two-sided one, as approximately shown in FIG. 8. In this case, when the raw material flows around the reactor on its external surface, low pressure zones arise, which contributes to the outflow of active hydrogen and / or light radicals from the surface of the reactor and prevents the buildup of raw materials on the surface of the reactor. In FIG. 9 is a vertical longitudinal section through a reactor in the form of an annular cylinder with a catalyst. Heated molecular hydrogen or hydrogen-containing fractions are fed into a transverse annular collector (Fig. 9, position 9), from which hydrogen or hydrogen-containing fractions through pores or holes (Fig. 9, position 10) of arbitrary shape and size fall into the volume with the catalyst (Fig. 9, item 11). The collector may be longitudinal (Fig. 10), or mixed, or of another shape. Active atomic hydrogen formed in the reactor (and radicals formed after the catalytic cracking of hydrogen-containing fractions) through the corresponding pores or holes on the external surfaces of the reactor with the catalyst (Fig. 9, 10, position 10) enters the reaction zone with the feed. The difference between this version of the reactor and the previous one (in the form of a rod cylinder) is that the raw material flows around the reactor from two sides (external and internal) and the interaction zone of hydrogen and raw materials is used more efficiently. Other forms of reactors (ball, in the form of plates, tubular coils and other figures) or packages of rods, ring cylinders, plates and reactors of another form can be used. In FIG. 11 to 13 show a cross section of a stack of rod reactors (FIG. 11), a stack of ring reactors (FIG. 12), and a reactor consisting of several ring reactors cylinders arranged coaxially (Fig. 13). The reactor packages, as well as individual reactors with a catalyst, can be located both along the flow of raw materials, and across or at an angle. The raw materials reacted with active hydrogen and / or light radicals can be sent immediately to obtain marketable products. If it is necessary to increase the yield of light target products to almost 100%, it is advisable to supplement the installation with a device for separating the reacted raw materials into light target reaction fractions, mainly with a boiling point up to 350-360 ⁰ C, and a heavy separation residue, mainly with a boiling point 360 ⁰ C and above. In FIG. 14 shows a vertical longitudinal section through a unit supplemented by a separation device (key 5). Typically, the simplest separation device is in the form of a capacitive apparatus in which, to increase the interfacial surface and more efficient separation of the gas-vapor and liquid phases, the reacted raw materials are dispersed with a decrease in pressure. The device is equipped with nozzles for the output of the vapor-gas phase (light target fractions) and the liquid phase (separation residue). Sometimes it is more efficient to attach a cracking device with a reactor with a catalyst to a separation device tangentially to its body (a horizontal cross section is shown in Fig. 15). Moreover, due to the formation of vortex motion in the casing of the separation device and pressure reduction in the inner part of the vortex, a more effective separation of the liquid and vapor-gas phases occurs. In addition, it is promising to use a well-known atmospheric distillation column as a separation device, in which the reacted feed is separated into the gas part, several narrow light fractions, and heavy distillation residue of the fuel oil type. In this case, part of the gas and light fractions (depending on the task and the purpose of processing) it is advisable to send to the beginning of the process together with hydrogen and / or hydrogen-containing media to obtain active atomic hydrogen and / or light radicals in order to save hydrogen and / or hydrogen-containing media coming from outside the process. The heavy residue or part thereof (depending on the task and the purpose of processing) is sent to the beginning of the process for reprocessing in order to increase the depth of further processing of raw materials and increase the yield of light target products.

It is easy to implement the proposed processing process both in industrial and in bench conditions. The feedstock used was heavy oil from the Middle Volga fields, as well as heavy oil from other fields and oil residues.

In simplified bench conditions, the feedstock is heated using an electric heater (Fig. 2, 3, position 1) and subjected to thermal cracking in a heated coil (Fig. 2, 3, position 2), while the stages and devices of heating and cracking are combined in one apparatus. The temperature at the stage and in the cracking device was in the range of 400-450 ⁰ C or more. Molecular hydrogen is supplied from the cylinder (at a higher pressure than the pressure in the cracking device, so that the feed does not enter the reactor with the catalyst) into the reactor (Fig. 2, 3, position 4) with the nickel, molybdenum or platinum catalyst in it (in the form granules with a diameter of up to 3 millimeters). Hydrogen and a reactor with a catalyst, which is located inside the heated feedstock in the cracking zone, are heated in this embodiment to the required temperature due to the heat of the heated feedstock. The reactor with the catalyst is arranged in the form of a rod cylinder, into which the catalyst is installed, installed in the heated feed stream, with hydrogen supply a pipe and a collector, with holes distributed over the surface of the reactor for distributing the resulting atomic hydrogen over the cross section and volume of the cracking zone. The design of the reactor with the catalyst can be cylindrical, annular, spherical, in the form of a plate, and so on, this is not of fundamental importance. In this particular case, a rod-type cylindrical reactor was used as the simplest to manufacture. Atomic hydrogen generated in a reactor with a catalyst enters directly into the cracking zone of the feedstock, where a saturation reaction of open radical bonds takes place. The reacted feed is cooled (not shown in the diagram for simplicity) and analyzed. The separation stage was not used in the experiments. In this embodiment, the stages and devices of heating and cracking the raw materials, heating hydrogen or hydrogen-containing media and a catalyst, producing active atomic hydrogen are combined in one apparatus. Some results are shown in table 1. The processing depth reaches 81%, and the sulfur content decreased by almost 10 times. The potential (content of light target fractions) of raw materials increased by more than 2 times, the amount of harmful impurities decreased significantly, i.e., the quality of raw materials for processing and obtaining marketable light products improved. With the addition of 4% shale crushed to the size of 0.05-1 micrometer in the initial oil, the yield of light target fractions increased to 82.7%, i.e. part of the solid hydrocarbons was processed into light liquid hydrocarbons. To achieve almost the same results in this method, instead of hydrogen, you can use propane - butane (the results are almost the same) a mixture of a balloon and other light products enriched with hydrogen or fractions. Table 1

When processing fuel oil (bottom residue after an atmospheric column) according to this method, the amount of light target fractions with a boiling point up to 360 ^° C was 67.3% of the mass, and in the initial fuel oil this amount was only 2.6% of the mass. This is understandable since light fractions are much more difficult to crack than heavy fractions consisting of long polyatomic molecules. In such a facility, using this method, it is possible to process heavy oil, fuel oil and other residues of oil refining and petrochemicals directly at the production site to produce high-potential and higher-quality oil (raw materials) for transportation to oil refineries and petrochemical plants for further processing and obtaining light target commodity products by known methods , or receive marketable products at the place of use of the proposed method, completing the installation with the necessary devices. For increasing the depth of processing requires multiple processing of the separation residue.

In conditions as close to industrial as possible, the proposed method is implemented on a bench installation with a capacity of up to 30 kg / h. A step-by-step diagram of a bench installation is shown in FIG. 2, the main nodes - in FIG. 14. The installation is equipped with various capacitive equipment for storing raw materials and collecting the resulting products, heat exchange equipment for heating the raw materials and the remainder of the separation and cooling of products, pumping equipment and instrumentation. Raw materials are pumped into the coil of the electric heater 1 (analogous to an industrial furnace), then the heated feed is fed to the stage and cracking device 2 (usually a portion of the heated coil). Hydrogen from the cylinder is heated (Fig. 2, position 3), passed through a heated reactor with catalyst 4, and also fed to the stage and cracking device (Fig. 2, 14, position 2), the reacted mixture is sent to the stage and to the separation device ( Fig. 2, 14, item 5), for example, is dispersed with decreasing pressure in a capacitive apparatus. In this embodiment, the stages and devices of heating and cracking the raw materials, heating hydrogen or hydrogen-containing media and a catalyst, producing active atomic hydrogen and separation are combined in one apparatus, and hydrogen or hydrogen-containing fractions and a reactor with a catalyst for producing atomic hydrogen are heated due to the temperature of the raw material and the residue separation. After the separation stage and device (Fig. 2, 14, position 5), the separation residue is completely returned to the beginning of the process for repeated repeated processing, although a branch pipe is provided for supplying part of the separation residue at the stage of obtaining heavy commercial products. The process is continuous. Some results obtained at the bench installation for the implementation of the proposed method are shown in table 2. The processing depth reaches 97%. Taking into account the formed non-condensed gases, one can confidently talk about almost 100% depth of processing of raw materials using this method.

table 2

To achieve almost the same results in this way, instead of hydrogen, you can use propane - butane mixture from a balloon and other light products enriched with hydrogen or fractions. When using a propane - butane mixture from a cylinder instead of hydrogen, the total yield of light target fractions practically did not change and amounted to 97.0% of the mass. The quantity of gasoline ^'fractions (having a boiling point up to 180 ⁰ C) decreased to 1.8 wt%, and the number of diesel fractions (having a boiling point of 240 ⁰ C to 360 ⁰ C) increased to 1.5% by weight, the amount of kerosene fractions (with a boiling point from 180 ⁰ C to 240 ⁰ C) practically did not change. With the addition of a propane - butane mixture in the feedstock up to 3%, the yield of the gasoline fraction increased insignificantly (up to 1%).

If you use the high reactivity of atomic hydrogen and / or light radicals, it is advisable to use the scheme of oil refining without cracking. The purified raw material (the cleaning stage is not shown) is supplied to the stage and the heating device (Fig. 2, 3, position 1), while the heating temperature of the raw material in these experiments did not exceed 400-420 ⁰ C, i.e. thermal cracking does not occur. Molecular hydrogen or propane-butane from the cylinder is fed to the heating stage (Fig. 2, position 3), then to the stage and device for producing atomic hydrogen and / or light radicals (Fig. 2, 3, position 4), the resulting atomic hydrogen and / or light radicals are fed to the stage and to the heating device (Fig. 2, 3, position 1). Then the reacted raw materials are cooled and analyzed (in the industrial version they are sent to obtain marketable products). Those. the process of preparation and deep processing of hydrocarbon raw materials can be carried out without cracking the raw materials, however, this process is still poorly studied, but has broad prospects, because can take place at lower temperatures and energy costs than with the implementation of thermal and / or thermomechanical cracking. Some results are presented in table 3.

Table 3

The results are good, although worse than in previous cases. The yield of light target fractions increased 1.48 times compared with the feedstock. A higher yield of the desired fractions can be obtained by using a stage and a separation device and repeated processing of the separation residue, as previously shown.

Thus, the industrial technical result is an increase in the yield of light target products or fractions (gas, gasoline, kerosene and diesel, as well as fractions for petrochemical and chemical industries) and, accordingly, an increase in the processing depth, an improvement in the quality of the obtained fractions for their further transportation and processing - achieved by such an organization of the preparation process and deep processing, in which the feedstock and the catalyst do not contact, as a result of which the catalyst does not it is poisoned by harmful impurities and practically does not coke, which leads to an increase in the durability of the catalyst and the absence of the need for regeneration processes, and the processing can be deepened to almost 100% by this method by repeated, possibly multiple, processing of the heavy part of the separation of reaction products. The proposed installation is easy to operate and does not require large capital and operating costs.

Using the proposed method and installation, it is easy to build highly efficient new and modernize existing oil refining and petrochemical plants to increase the depth of processing and yield the most valuable light commercial products.

Claims

Claim

1. The method of preparation and deep processing of hydrocarbon raw materials, including heating the raw material, obtaining final products, characterized in that the liquid (for example, oil, fuel oil, residues of oil refining and petrochemicals), the feedstock is heated to a temperature above 20-50 ⁰ C or heated and subjected thermal and / or thermomechanical (non-catalytic) cracking, molecular hydrogen or light hydrogen-containing media enriched with hydrogen, for example, natural or associated gas, gas and light fractions of oil refining and petrochemicals, in particular and the gas and light fractions obtained in the processing process according to this method, if necessary, are heated separately from the feedstock, sent at a higher pressure than the pressure in the heating and / or cracking stage, to the stage of producing active atomic hydrogen and / or light radicals into the reactor or a package of reactors with a catalyst heated to the required temperature, after which the resulting active hydrogen and / or light radicals are sent to the heating and / or cracking zone of the feed for the reaction, the reaction products are sent to the floor stage eniya commercial products or to the separation stage in which the end of the reaction, the target light reaction fraction after the separation step, preferably a final boiling point up to 350-360 ⁰ C, partly or entirely directed to the step of producing a target light commodity type products LPG, gasoline , kerosene, diesel fuel, products petrochemistry at the place of processing of raw materials according to this method, or after cooling is transported to a remote place for the production of light commercial products, and / or partially returned to the beginning of the process in a reactor with a catalyst to produce active atomic hydrogen and / or light radicals, and / or partially returned and is introduced into the feedstock, the heavy residue after the separation stage, mainly with a boiling point of 360 ^° C or higher, is partially or completely directed to produce heavy commercial products such as bitumen, coke, and / or partially or completely sent for re-processing according to this method to the beginning of the process together with the feedstock or separately to the next processing stage, the ratio of the surface of the reactor or reactors with the catalyst to the volume of the heating and / or cracking zone of the raw material should be increased so as to maximize the interaction area (reactions) of atomic hydrogen and / or light radicals and heated or cracked raw materials for the efficient use of 'reactive products. _t .

2. The method according to p. 1, characterized in that the number obtained in the reactor or reactors with a catalyst of hydrogen atoms and / or light radicals must exceed the number of open bonds of the cracking radicals of raw materials.

3. The method according to p. 1, characterized in that the solid hydrocarbons (for example, coal, shale, vegetable products) are sent to the stage of fine grinding and introduced into the feedstock and / or heavy separation residue before its ^" reprocessing, gaseous hydrocarbons are also injected into feedstock and / or separation residue before reprocessing.

4. The method according to p. 1, characterized in that the stage of heating and / or cracking of the feedstock and / or the residue of separation, heating of hydrogen or hydrogen-containing media and catalyst, obtaining active atomic hydrogen and / or light radicals and separation into light part and heavy residue combined in one device.

5. The method according to p. 1, characterized in that the heating of hydrogen and / or hydrogen-containing media and the catalyst at the stage of producing active atomic hydrogen and / or light radicals is carried out due to the heat of the heated feedstock and / or separation residue.

6. The method according to p. 1, characterized in that the stage of producing atomic active hydrogen and / or light radicals is carried out using radioactive radiation, wave action on hydrogen and hydrogen-containing media with a wide range of frequencies of various nature and intensity, as well as using chemical reactions.

7. The method according to p. 1, characterized in that gaseous hydrocarbons are used as the feedstock, and gaseous hydrocarbons can be used as a coolant and a carrier in the processing of solid hydrocarbons in the form of fine powders, as well as liquid hydrocarbons.

8. The method according to p. 1, characterized in that non-hydrocarbon substances, in particular water and / or water vapor, are used as hydrogen-containing media to produce atomic hydrogen.

9. The method according to p. 1, characterized in that at the stage of separation using a distillation column.

10. The method according to p. 1, characterized in that the light target reaction fractions after the separation stage are directed to the stage of separation of part of the gas and light fractions, as well as unreacted hydrogen and / or light hydrogen-containing starting media, which together return to the beginning of the process to obtain atomic hydrogen and / or light radicals, and / or partially returned and introduced into the feedstock.

11. The method according to p. 1 or 10, characterized in that the separation residue before reprocessing, as well as unreacted hydrogen and / or light hydrogen-containing starting media and part of the gas and light fractions that are returned to the beginning of the process to produce atomic hydrogen and / or light radicals, are purified from harmful impurities and compounds.

12. Installation for the preparation and deep processing of hydrocarbon feedstock, including a device for heating the feedstock, a device for producing final products, characterized in that the heating device and / or thermal and / or thermomechanical (non-catalytic) cracking of the feedstock further comprises a reactor or reactor pack with a catalyst to obtain active atomic hydrogen and / or light radicals from molecular hydrogen and / or light hydrogen-containing media enriched with hydrogen, for example, natural or th gas, gas and light fractions of petroleum refining and petrochemistry, particularly gas and light fractions produced in the recycling process of the present method, the reactor if necessary to produce atomic hydrogen and / or light radicals is equipped with devices for heating hydrogen-containing media and a catalyst, moreover, the pressure in the reactor with the catalyst is greater than the pressure in the heating and / or cracking device, the reactor with the catalyst is made in the form of a cylinder, a ball, an annular cylinder, a parallelepiped (plate), a tubular coil or other volumetric figure with a catalyst placed in it in the form of granules of arbitrary size and shape, the surface of the reactor with the catalyst is made of a material that is freely permeable to active atomic hydrogen and / or light radicals, or holes of arbitrary shape are made on the surface of the reactor, the hole sizes are smaller than the size of the catalyst granules, more than one reactor or reactor package with a catalyst can be placed in the cracking device, and the ratio of the surface of the reactor or reactors with the catalyst to the volume of the zone of heating and / or cracking of raw materials should be increased so as to maximize the interaction (reaction) of atomic hydrogen and / or light radicals and heated or cracked raw materials for ffektivnogo use of reactive products.

13. Installation according to p. 12, characterized in that the number obtained in the reactor or reactors with a catalyst of hydrogen atoms and / or light radicals must exceed the number of open bonds of the cracking radicals of the feedstock.

14. Installation according to claim 12, characterized in that a collector with holes for distributing molecular hydrogen and / or hydrogen-containing media over the cross section and volume of the reactor is made inside the reactor with the catalyst.

15. Installation according to claim 12 or 14, characterized in that the walls of the collector and the reactor with the catalyst are made of porous material with arbitrary pore sizes, for example, in the nanometer range.

16. Installation according to p. 12, characterized in that the heating of hydrogen or hydrogen-containing media and a catalyst in a device for producing active atomic hydrogen and / or light radicals is carried out due to the heat of the heated feedstock and / or separation residue.

17. Installation according to claim 12, characterized in that the reactor with the catalyst or reactor packages can be located either along the movement of the feed stream, or across or in an intermediate position.

18. Installation according to p. 12, characterized in that the reactor with the catalyst has a smoothed surface shape for better flow around the feed, for example one in which the outer surface has the shape of an aerodynamic wing, especially a two-sided one.

19. Installation according to p. 12, characterized in that the reactor shell or the entire reactor is made entirely of material that is a catalyst for carrying out the process of producing atomic hydrogen and / or light radicals from molecular hydrogen and / or hydrogen-containing media.

20. Installation according to p. 12, characterized in that the heating device and / or cracking of the feedstock with the reactor with the catalyst is communicated with the separation device, in which the reaction is completed, light target reaction fractions after the separation device, mainly with a boiling point up to 350-360 ⁰ C, partially or completely sent to the stage of obtaining light target commercial products such as liquefied gas, gasoline, kerosene, diesel fuel, petrochemical products at the place of processing of raw materials by this method, or after cooling, they are transported to a remote place of receipt of light commercial products, and / or partially returned to the beginning of the process in a reactor with a catalyst to produce active atomic hydrogen and / or light radicals, and / or partially returned and introduced into the feedstock, the heavy residue after the device separation, mainly with a boiling point of 360 ⁰ C and above, partially or completely sent to obtain heavy commercial products such as bitumen, coke, and / or partially or completely sent for re-processing according to this method at the beginning of the process together with the feedstock or separately to next processing setup.

21. Installation according to p. 20, characterized in that the device for heating and / or cracking the raw materials and / or the residue of separation, heating of hydrogen or hydrogen-containing media and a catalyst, producing active atomic hydrogen and / or light radicals and separation into light part and heavy residue combined in one device.

22. Installation according to claim 12 or 20, characterized in that for processing solid hydrocarbon raw materials (for example, coal, slate, vegetable products), the installation further comprises a device for finely grinding solid hydrocarbon raw materials, after which the crushed hydrocarbons are introduced into the feedstock and / or heavy separation residue before reprocessing.

23. Installation according to p. 12 or 20, characterized in that it further comprises a device for separating unreacted hydrogen and / or light hydrogen-containing starting media, as well as parts of the gas and light fractions of the process after the separation device, which together return to the beginning of the process to produce atomic hydrogen and / or light radicals, and / or partially returned and introduced into the feedstock.

24. The installation according to p. 12 or 20, characterized in that it further comprises a device for purification from harmful impurities and compounds of the separation residue before re-processing it, as well as unreacted hydrogen and / or light hydrogen-containing starting media and parts of gas and light fractions, before returning to the beginning of the process to produce atomic hydrogen and / or light radicals.

25. Installation according to claim 20, characterized in that a distillation column is used as a separation device.