RU78793U1 - SCHEME FOR PREPARATION AND IN-DEPTH PROCESSING OF HYDROCARBON RAW MATERIALS - Google Patents

Abstract

1. Scheme for the preparation and in-depth processing of hydrocarbon feedstocks, including blocks for purifying raw materials from harmful impurities, heating the feedstock and hydrogen and feeding them to a reactor with a catalyst, as well as production units for commercial products, characterized in that it is liquid (for example, oil, oil residues and other) the feedstock after the block from harmful impurities is sent to the heating block or to the heating block and thermal and / or thermomechanical cracking and fed to the reactor-mixer without catalyst, molecular hydrogen or light hydrogen-containing hydrogen-enriched media, for example, natural or associated gas, in particular gas and light shoulder straps of gasoline fractions obtained in the preparation process, if necessary, are heated separately from the raw materials in the heating block of hydrogen or hydrogen-containing media, sent at a higher pressure than the pressure in the reactor -mixer, to obtain active atomic hydrogen in a reactor with a catalyst heated to the required temperature, after which the active hydrogen is sent to the mixing reactor in the cracking zone for intensive mixing to raw materials and active hydrogen for the reaction, the reaction products after the mixing reactor are sent to the separation unit, light target reaction fractions with a boiling point up to 360 ° С are mainly sent to the target product unit such as liquefied gas, gasoline, kerosene, diesel fuel , petrochemical products, etc. to the place of preparation and processing of raw materials according to this utility model or transported to a remote place for receiving light commercial products, the heavy residue after the separation stage

Description

The utility model relates to the oil refining and chemical industries, and specifically to the field of preparation and advanced oil refining, including heavy oil, residues of oil refining and petrochemical industries, coal, oil shale, plant 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. The preparation of oil, oil residues and other raw materials for processing refers not only to the removal of harmful impurities from raw materials, but also, most importantly, an increase in the number of light target products higher than their potential content in the feedstock, which allows to further significantly increase the processing depth and profitability of the whole processing industry. Light target intermediates or fractions are understood as fractions for further processing and obtaining light target commodity products with a boiling point mainly up to 360 ° С, containing fuel, i.e. the most expensive gas, gasoline, kerosene and diesel fractions, as well as intermediates for petrochemical and chemical industries. In the future - light target fractions or intermediates, from which, upon final processing, light target products are obtained (liquefied gas, gasoline, diesel fuel, petrochemical products, etc.).

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.

The potential of high-quality raw materials is almost 80% realized, while retaining only the prospects of small discoveries. So, for example, in Tatarstan for a long time the preparation of oil reserves is carried out at the expense of small fields and oil of deteriorated quality. More than 30% of the reserves are represented by high viscosity oil. In the Perm Region, the structure of oil reserves is generally complex due to the large share of heavy oil (58%).

In the Ulyanovsk region, 41 oil fields have been discovered, their total proven reserves amount to 50 million tons, and they are represented by heavy and highly viscous oils. A similar situation in Udmurtia, etc. In general, in the Ural-Volga region, as in other regions of the country, it will be necessary to deal more and more actively with carbon oil and natural bitumen. Reserves and production of heavy oil prevail in all countries of South America, Mexico, Canada, Africa, China and in many countries of different continents. Such oil is even transported through the pipeline with the addition of a sufficient amount of expensive solvent.

Processing heavy viscous sulphurous oil is very difficult, energy-intensive and, as a result, low-profitable or unprofitable. It contains a low amount of "light" (fuel) fractions. In plants with a classical scheme, it is possible to select these fractions with respect to oil no more than 25-30%. The high content of sulfur, chlorides and resinous substances reduces the life of the equipment of oil refineries. For example, the properties of the "heavy" Ulyanovsk oil are as follows: density - 930-980 kg / m ³ (20-13 API), viscosity - 50-90 mPa · s, sulfur content - up to 5% wt., Chloride salts up to 2000 mg / l, resins and asphaltenes - up to 35% of the mass.

The decrease in light oil reserves of traditional fields increases interest in the production and, consequently, in the processing of heavy oil (Ratov AN, Nemirovskaya GB and other problems of oil development in the Ulyanovsk region. "Chemistry and technology of fuels and oils", No. 4 , 1995). As a rule, heavy oil is understood to mean oil with a density of more than 900 kg / m ³ , with a low content of light fractions and a high content of tar-asphaltene substances and other harmful impurities. These features of the composition of heavy oil cause serious difficulties both in production and transportation: high viscosity and pour points, and during its processing: a significant content of various impurities, resins. Transportation is significantly complicated due to the high viscosity of the raw materials, the high content of resinous and asphaltene substances and paraffin, and deposits on the working surfaces of the equipment is the reason for its failure. And sulfur and metal compounds, especially vanadium, as well as chloride salts, usually found in such oil, have an increased corrosive effect on the equipment of oil refineries. In addition, the content of light target products in heavy oil is small, and without additional deepening processes, the processing of such oil is unprofitable.

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 processing depth of classical raw materials for these purposes - oil and oil residues, solid and gaseous hydrocarbons, which is what the proposed application for a utility model is aimed at.

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 the 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 and other harmful impurities (Erich VN, Rasina MG, Rudin MG "Chemistry and oil and gas technology ". Leningrad," Chemistry ", 1972. Skoblo AI, Tregubova IA, Egorov NN" Processes and apparatuses, oil refining and petrochemical industries. Moscow, State Scientific and Technical Publishing. , 1962. Sudo M. M. “Oil and combustible gases in the modern world.” Moscow, Nedra, 1984. Rabinovich G. P., Ryabykh P. M., Khokhr Yakov PA, under the editorship of Sudakov EN “Calculations of the main processes and apparatuses for oil refining.” Reference book. Moscow, “Chemistry”, 1979. Dryatskaya Z.V., Mkhchiyan M.A., Zhmykhova N.M. and others. "USSR Oil. Volume 4". Moscow, "Chemistry", 1974. Levchenko D.N., Bergshtein N.V., Pinkovsky Y.I. Desalting of oil at oil refineries: Overview. - M .: TSNIITENeftekhim , 1973. Levchenko D.N., Bergstein N.V., Nikolaeva N.M. Oil desalination technology at oil refineries. - M .: Chemistry, 1985. Gershuni S.Sh. Modernization of electric dehydrators ways to increase the efficiency of their use: Overview. - M.: TSNIITENeftekhim, 1986).

However, using these methods and schemes, only the raw materials are cleaned from harmful impurities, and the fractional composition of the raw materials does not change, therefore, for the cost-effective processing of heavy raw materials (oil, various oil residues, etc.), these processes are clearly not enough, processes that allow for further processing to receive an increased 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 well-known hydrotreating process, gasoline, kerosene and diesel fuel that have already been separated out are cleaned, but not heavy raw materials.

Known processes of thermal cracking for advanced processing of raw materials (Benson S, Thermochemical kinetics, trans. From English, under the editorship of N.S. Yenikolopyan, M., Mir, 1971, Krasyukov A.F., 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, etc. ) 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, etc. 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, etc. 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 ° 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. In addition, using thermal cracking it is not possible to achieve 100% processing depth, because heavy residues such as coke will always remain.

Known processes for the processing of heavy oil-containing fractions using, simultaneously with thermal, and wave, including cavitation, exposure of various nature and a wide range of frequencies, which can be defined as methods or processes of thermomechanical exposure or cracking.

There is a known process of processing by sequential extraction of fractions from hydrocarbons using electromagnetic energy with a frequency of 300 MHz-300 GHz (US patent 5055180, class C10G 1/00, 1991).

In the known process of processing fuel oil by vacuum distillation to obtain distillate fractions, the liquid phase of the still bottom is affected by acoustic vibrations with a frequency of 0.1-200 KHz and a power of 0.2-3 W / cm ² at a residual pressure of 20-200 mm Hg ( see ed. St. USSR 1377281, class C10G 7/06, 1988).

The process of cracking petroleum products using the ultrasonic frequency spectrum is also known. According to this process, the feed (oil-containing product) and dispersant are fed into the zone

processing, 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 (see RF patent 2078116, C10G 15/00, 1995).

However, these processes have so far been implemented only in the laboratory version and have not found application 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 such as fuel oil, coke, etc. always remain. In addition, if heat is directly used to activate vibrational levels of molecules when raw materials are activated by direct heating, and to activate those But for molecules with a wave action, it is first necessary to spend heat (energy) on creating a wave effect, and this process has a very low efficiency, then the energy costs for implementing this process 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.

The most famous and widely used processes of deep processing are catalytic - catalytic cracking, hydrocracking, etc. (Sukhanov V.P. Catalytic processes in oil refining. M., "Chemistry", 1973. Prokopyuk S.G., Masagutov PM Industrial catalytic cracking units M., Chemistry, 1974.) The essence of catalytic cracking is that bond breaking occurs in the presence of a catalyst at high temperature (450-550 ° C and above) and pressure (up to 15 MPa), which leads to serious increase in capital costs, with g drokrekinge - in a hydrogen atmosphere. Catalytic cracking and hydrocracking in various versions (with a stationary catalyst, with a fluidized catalyst bed, etc., 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 etc.). In the processes of catalytic cracking, the feedstock, and during hydrocracking, the feedstock and hydrogen are heated and sent to a reactor with a catalyst, then the reaction products are sent to a 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 efficiency of the processing complex, it is necessary to use processes and equipment for the regeneration or replacement of spent catalyst, which ultimately leads to

significantly complicating and increasing the cost of process equipment, current and capital costs, complicating 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 currently 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 using 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 purpose of the utility model is to increase the yield of light target intermediates or fractions (gas, gasoline, kerosene and diesel, as well as fractions for petrochemical and chemical industries) up to 100% and, accordingly, increase the processing depth to 100%, purify raw materials from sulfur and other harmful impurities, preventing coking and poisoning of the process catalyst with raw materials and its impurities, reducing operating and capital costs, simplicity and reliability of equipment design and process control and regulation, continuously process, improving the quality of the obtained fractions for their further transportation and processing, as well as the optimal and rational use of raw materials in their further processing and obtaining the target marketable products. Light target products are understood as processing fractions with a boiling point predominantly up to 360 ° С, containing fuel, i.e. the most expensive gas, gasoline, kerosene and diesel fractions, as well as intermediates for petrochemical and chemical industries.

The technical result, the proposed utility model is aimed at, and the goal is achieved by organizing a process scheme in which the feed and the catalyst do not contact, as a result of which the catalyst is 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 or its part is subjected to the processing process according to this utility model repeatedly. Liquid (for example, oil, oil residues, etc.) feedstock after a purification unit (dehydration, desalination, purification from mechanical impurities, etc.) is sent to a heating unit or to a heating unit and thermal and / or thermomechanical cracking and fed to a reactor-mixer without a catalyst, molecular hydrogen or light hydrogen-containing media enriched with hydrogen, for example, associated gas, natural gas, including gas obtained in the preparation process, pentane fractions,

xylene, toluene, light shoulder straps of gasoline fractions, including those obtained during the preparation, etc., if necessary (especially if the hydrogen-containing raw materials are liquid and must be transferred to the vapor-gas phase) are heated in a hydrogen or hydrogen-containing heating block media separately from the raw material, is directed at a pressure higher than the pressure in the mixer reactor to produce active atomic hydrogen into a reactor with a catalyst heated to the required temperature (atomic hydrogen production unit), after which active hydrogen sent to the mixing reactor in the cracking zone for intensive mixing of the cracked feed and active hydrogen for the reaction, the reaction products after the mixing reactor are sent to the separation unit, light target reaction fractions, mainly with a boiling point of up to 360 ° С, are sent to the receiving unit target commercial products such as liquefied gas, gasoline, kerosene, diesel fuel, petrochemical products, etc. at the place of preparation of raw materials according to this utility model or transported to a remote processing site ki of obtaining light commercial products, the heavy residue after the separation stage, mainly with a boiling point of 360 ° C, is sent to the block for the production of heavy commercial products such as bitumen, coke, etc., or partially or completely sent to the purification unit from harmful impurities, then re-processing according to this utility model at the beginning of the process together with the feedstock or separately to the next stage of processing, solid hydrocarbon raw materials (for example, coal, slate, vegetable products, etc.) are sent to fine grinding pulp and injected into the feedstock and / or heavy separation residue before it is processed again, gaseous hydrocarbons are also introduced into the feedstock and / or separation residue before it is processed again, liquid, solid and gaseous hydrocarbons can be processed according to this scheme simultaneously, according to individually or in pairs, the blocks of heating and cracking of raw materials, heating of hydrogen or hydrogen-containing media and a catalyst, the production of active atomic hydrogen, mixing cracked raw materials with active nym hydrogen and separation on unreacted light portion and a heavy residue may be combined in one apparatus. The temperature of 360 ° 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 utility model, the changing requirements are easy to satisfy by changing the process temperature accordingly at the separation stage.

The problem is achieved by the fact that gaseous molecular hydrogen or light hydrogen-containing fractions enriched directly in contact with the heated catalyst

hydrogen, for example, associated or natural gas, or a process gas, methane, propane - butane mixtures, pentane fractions, xylene, toluene, light shoulder straps of gasoline fractions, including process fractions, etc., used to produce active atomic hydrogen, which then reacts with the raw material heated to a certain temperature. Hydrogen-containing fractions and 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, etc., as well as harmful impurities, and their interaction with the catalyst does not lead to its coking and poisoning. The process of formation of atomic hydrogen must be carried out in such modes so that when a hydrogen atom is disconnected, a hydrocarbon radical is formed, and not pure carbon. 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. there is a decrease in capital and operating costs, the processing depth can be increased to 100%. At the same time, 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 for their further processing in the implementation of this scheme.

The feed is heated separately from hydrogen or hydrogen-containing products, and it is heated to a temperature at which thermal or thermomechanical cracking of the feed is somewhat feasible.

Thermal cracking for heavy oil has features: the decomposition onset temperature is 238 ° C at a residual pressure of 0.25 kPa (Soskind D.M., Ratov A.N. Small-tonnage complex for the processing of oils of the Ulyanovsk Region with associated vanadium recovery. "Chemistry and Technology fuels and oils ", No. 1, 1996). Starting from 410-420 ° С and more, thermal cracking proceeds at a high speed, i.e. on an industrial scale. 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, the lower the temperature of the process, the more isomers and aromatic compounds, but at the same time to achieve a greater depth of conversion of the raw material, more than one processing is necessary.

In thermomechanical cracking, the feed is heated thermally, i.e. the most economical in this case, a method up to a certain temperature, which is lower than the temperature of the onset of an avalanche-like uncontrolled thermal cracking, i.e. heated so that uncontrolled thermal cracking has not yet begun. Heating can

to be carried out in a fire or electric furnace, or another type of furnace, as well as in heat exchangers of various designs, in which the raw material is heated by a heat carrier. Raw materials heated (for example, by a coolant) to subcritical temperature (vibrational levels of molecules are already excited, but there is still no avalanche-like breaking of molecules due to this excitation) is subjected to mechanical (for example, cavitation) and wave action of various nature (sound, ultrasound, cavitation, electromagnetic, light, radiation, etc.) and a wide range of resonant frequencies.

The raw materials processed by thermal or thermomechanical action are sent to the mixer reactor for intensive mixing with active atomic hydrogen, and the thermal or thermomechanical effect can be structurally implemented in the mixer reactor, i.e. cracking of raw materials and mixing them with atomic hydrogen can be combined in one apparatus. The reaction products after the reactor-mixer are sent to a separation unit for light target reaction fractions, mainly with a boiling point of up to 360 ° C, and a heavy separation residue.

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 reaction products with open bonds in the future, upon receipt of marketable products or transportation, in contact with air, for example, oxygen can be added, 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, 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 are obtained as good raw materials for the chemical industry.

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 (Cu, Pb, Ag, etc.) from their salts and enters

other chemical reactions that ordinary molecular hydrogen is not capable of under the same conditions. In chemical interactions involving ordinary hydrogen, its molecule must decay into atoms. But the very reaction of such a decay (dissociation into atoms) is strongly endothermic. The energy spent on the dissociation of one hydrogen molecule into two atoms is 435 kJ (kilojoules). Obviously, the energy expended on this reaction (dissociation energy) must be replenished by the energy released during the interaction of hydrogen atoms with the substance introduced into the reaction. Therefore, it can be expected that hydrogen reactions, in which less than 435 kJ / mol is released, will not occur spontaneously. In the case of the interaction of substances with atomic hydrogen, such an energy expenditure for dissociation is no longer required. Therefore, a much wider range of reactions is possible here. The large amount of energy released during the formation of a hydrogen molecule explains its stability under ordinary conditions. 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. The rate of reactions of the formation of atomic hydrogen from molecular and light hydrogen-containing media increases when using catalysts (platinum group metals, transition or heavy metal oxides), methods of excitation by means of wave action with a wide range of frequencies of various nature and intensity (light, electric discharge, electric arc, etc. .), as well as through 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). Therefore, it reacts with hydrocarbon molecules, and not just with radicals. Those. the process of preparing hydrocarbon feedstock for further in-depth processing can be carried out without cracking the feedstock, but this process is still poorly understood, but has broad prospects, as can take place at lower temperatures and energy costs than with the implementation of thermal and / or thermomechanical cracking.

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

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 ° C or more. In this case, during the interaction of hydrogen and hydrogen-containing media with molybdenum, cobalt, zinc, vanadium, nickel and other catalysts, for example, based on aluminum oxide, or catalysts of a different type, atomic hydrogen is formed, which effectively saturates open bonds of light radicals resulting from the reaction cracking of hydrocarbons, resulting in the formation of saturated light target fractions of good quality. 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 according to this utility model, or partially or completely to obtain heavy commercial products such as coke, bitumen, etc. . (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. Moreover, the separation residue can be sent for re-processing at the beginning of the process together with the feedstock, or separately for an additional processing unit according to this utility model. 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 feedstock, and thermal or thermomechanical cracking of the feedstock is carried out 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 before the residue is processed again, it must be cleaned. With repeated reprocessing of the heavy separation residue, the feed will be processed into light target products with an efficiency of up to 100%.

Hydrogen-containing media and a reactor with a catalyst can be heated to produce atomic hydrogen 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 the reaction of thermal and / or thermomechanical cracking

usually exceeds 400 ° 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 this case, the blocks for heating and cracking the feedstock, as well as for heating hydrogen or hydrogen-containing media and the reactor with the catalyst, can be combined in one apparatus.

In addition to increasing the processing depth during the implementation of the proposed scheme, the feedstock is purified from sulfur and other impurities. The energy of the carbon-heteroatom bonds (carbon-sulfur, carbon-nitrogen, etc.) is lower than the carbon-carbon and carbon-hydrogen bonds (T.V. Bukharkina, N.G. Digurov. Chemistry of natural energy carriers 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 utility model 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 unit, mainly with a boiling point of up to 360 ° C, which are mainly in gas-vapor and droplet form, contain gas, gasoline, kerosene and diesel fractions, as well as fractions for the production of chemical products. The separation unit can be made in the form of a capacitive apparatus in which the raw material after the reactor-mixer is dispersed with a decrease in pressure and a significant increase in the interphase surface of the separated media to optimize the separation process. 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 part of the separation is a light product enriched in hydrogen, and can be partially or completely used at the stage of production of atomic hydrogen 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 preparing raw materials according to this scheme can be used. This leads to a partial saving of molecular hydrogen and hydrogen-containing fractions coming from outside the process. The remaining target fractions are sent to the unit for obtaining target commercial products such as gasoline, kerosene, diesel fuel, petrochemical products, etc. at the place of preparation and processing of raw materials according to this utility model, or, after cooling and condensation, are transported to a remote place for receiving light commercial products.

The utility model can be used for the preparation and further in-depth processing of solid and gaseous hydrocarbons.

Solid hydrocarbon feedstocks (e.g. coal, shale, vegetable products, etc.) are preliminarily crushed into a fine powder and introduced into a liquid feedstock and / or into the separation residue before it is processed again in accordance with this utility model. 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 in the separation unit and used to produce light target commodity products, heavy ones will be returned for reprocessing, and upon repeated processing, 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 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 ones, the separation residue must be cleaned from them before reprocessing, for example, by the same methods as the feedstock from mechanical impurities.

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 doing great harm to the environment and destroying valuable hydrocarbons. This model allows the efficient use of such hydrocarbons, mixing them into the initial liquid raw material and / or heavy separation residue during its reprocessing (similar to the processing of solid hydrocarbon raw materials in the form of a fine powder), or use them 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 similar to liquid feedstock. In this case, gaseous hydrocarbons can be used as heat and carrier in the processing of solid hydrocarbons in the form of fine powders.

Depending on the task, according to this utility model, it is possible to process liquid, solid, gaseous raw materials at the same time, or in pairs, or separately liquid or gaseous hydrocarbons. If, for example, the raw material is light oil or gas condensate, then it is optimal to first isolate light target fractions from the raw material from the distillation column, and send bottoms after separation for advanced processing according to this utility model.

In figures 1-6 presents enlarged schematic diagrams of the preparation and processing of hydrocarbons.

Figure 1-6 indicated: 1 - block heating and cracking of raw materials; 2 - reactor-mixer; 3 - block heating of hydrogen or hydrogen-containing media; 4 - unit for producing atomic hydrogen (reactor with catalyst); 5 - separation unit; 6 - unit for the preparation of light target commercial products (gasoline, kerosene, diesel fuel, petrochemical products, etc. - reforming, platforming, etc.); 7 - unit for the preparation of heavy commercial products (bitumen, bitumen emulsions, coatings, coke, etc.); 8 - block finely divided solid hydrocarbons; 9 - block heating and cracking the remainder of the separation; 10 - block heating of raw materials with the remainder of the separation and thermomechanical (acoustic, cavitation, etc.) processing; 11 - reactor-mixer of active hydrogen and cracked separation residue. The block of preliminary cleaning of raw materials (degassing, dehydration, desalination, purification from mechanical and other harmful impurities) is not shown in the figures for simplicity. Units for the production of commercial products usually include the following well-known processes: hydrotreating, reforming, platforming, etc., processes of the petrochemical and chemical industries, or at the first stage a compounding unit, a bitumen block for the production of oxidized bitumen, or a bitumen block combined with a vacuum block for the production non-oxidized bitumen, as well as equipment for the production of bitumen coatings, emulsions, boiler fuel, coke and other commercial products (Handbook of Petrochemistry. In two volumes. Volume 1, under. re . Ogorodnikov SK L., Chemistry, 1978, s.53-55).

If the raw material is heavy oil or oil residues (fuel oil, oil sludge, waste oil, etc.), then it is advisable to use the scheme of oil refining, presented in figure 1. The purified raw materials (the cleaning unit is not shown) is supplied to the heating and cracking unit (Fig. 1, position 1), then to the reactor-mixer (Fig. 1, position 2). Hydrogen or light hydrogen-containing media is supplied to the heating unit (Fig. 1, position 3), then to the atomic hydrogen production unit (Fig. 1, position 4), the obtained atomic hydrogen is fed to the mixing reactor (Fig. 1, position 5), where it is mixed with cracked raw materials and saturation of open bonds of radicals. After the reactor, the mixer reacted raw material is fed to the separation unit (Fig. 1, position 5), in which it is separated into light target reaction fractions, mainly with a boiling point of up to 360 ° С, which are transported to the place of receipt of light commercial products, and a heavy residue , mainly with a boiling point of 360 ° C, which is sent to the beginning of the process for repeated re-processing together with the feedstock.

If it is necessary to receive marketable products locally, i.e. to carry out a full processing cycle according to this model, it is advisable to use the scheme shown in figure 2. After block

separation (figure 2, position 5), light target fractions are sent to the block receiving the target marketable products (figure 2, position 6), such as liquefied gas, gasoline, kerosene, diesel fuel, petrochemical products, etc., heavy residue partially or completely sent to the block for the production of heavy commercial products (figure 2, position 7) such as bitumen, coke, etc., and / or partially or completely sent for re-processing according to this utility model at the beginning of the process together with the feedstock. In addition to the processing of gaseous hydrocarbons to liquid raw materials, they are introduced into the feedstock and / or residue during its reprocessing.

If, together with liquid raw materials, it is necessary to process solid hydrocarbon raw materials, then it is advisable to use the scheme shown in figure 3. Solid hydrocarbon feed is fed to the fine grinding unit (Fig. 3, item 8), then it is introduced into the feed liquid and / or the remainder of the separation before it is processed again. When using solid hydrocarbon feedstocks, it must be taken into account that it contains a lot of impurities, inorganic in particular, therefore, it must be cleaned before recycling the separation residue (the purification unit is not shown in the diagram for simplicity), for example, as well as the raw materials are cleaned of mechanical impurities.

The raw materials and the separation residue have different compositions and properties, and sometimes it is advisable to heat and crack them at different temperatures and thermal and / or thermomechanical processing conditions. In this case, the separation residue is fed to an independent heating and cracking unit of the separation residue separate from the raw material (Fig. 4, position 9), after which it is sent to the reactor-mixer (Fig. 4, position 2), into which the cracked raw material is also sent.

The heavy separation residue has a much higher boiling point than the feedstock, does not contain light fractions, so it can be heated in a separate heater (furnace) to a higher temperature. Then this heat can be used for heating and cracking raw materials. Such a circuit is shown in FIG. The raw material is heated to a low temperature (150-200 ° C) in order to reduce its viscosity, and then enters the heating and thermomechanical (acoustic, cavitation, etc.) processing unit of the raw material by the separation residue (Fig. 5, position 10). The heated residue (Fig. 5, position 9) to a high temperature (400-450 ° C or more) of the separation residue also flows there. The raw materials in block 10 due to the heat of the separation residue are heated to a high temperature and subjected to thermal and / or thermomechanical cracking. Heat exchange can be carried out using heat exchangers of various types, including through direct contact of the raw material and the separation residue. For cavitation processing of heated raw materials and applying acoustic effects to it, various devices are used: hydrodynamic devices, rotary pulsation apparatuses (RPA), etc. It’s best to use such special devices,

the action of which is based on the hydrodynamic effects of the medium moving at high speed through channels with obstacles and turns of various shapes, which leads to the appearance of local zones of reduced pressure, in which the process of evaporation and separation of the light cracking phase is more intense. With this approach, the cavitation and acoustic treatment process occurs in the entire volume of the treatment zone. Then the raw material or a mixture of raw materials and the separation residue is sent to the reactor-mixer (figure 5, position 2) and then according to the standard scheme. In this case, the blocks of heating and cracking of the raw materials, mixing the cracked raw materials with active hydrogen and separation into the light part and the heavy residue can be combined in one apparatus.

If the feedstock and the separation residue are heated and cracked separately, it is sometimes advisable to carry out the reaction with hydrogen in separate independent blocks, because this can lead to various reaction products. Such a circuit is shown in Fig.6. The raw material is heated, cracked and reacted with active hydrogen in a standard chain (Fig. 6, positions 1, 2), the separation residue is heated and cracked in a separate block (Fig. 6, position 9), then fed to a separate mixer reactor ( 6, position 11). The reaction products of the raw materials and the separation residue are sent to the common separation unit (Fig.6, position 5), then, if necessary, to the units for obtaining marketable products (Fig.6, position 6, 7). If necessary, you can create a completely separate chain for processing the remainder of the separation, including both a separate separation unit, and independent separate blocks for obtaining marketable products.

It is easy to implement the proposed processing process both in industrial and in laboratory and bench conditions. As the source of raw materials used oil field Vishenskoye Ulyanovsk region. (Ratov AN, Nemirovskaya GB and other problems of oil development in the Ulyanovsk region. "Chemistry and technology of fuels and oils", No. 4, 1995), as well as heavy oil from other fields and oil residues.

In laboratory conditions, the feedstock is heated under pressure in a cylindrical tank apparatus (reactor-mixer) with a diameter of 96 millimeters and a height of 400 millimeters, the apparatus is thermally insulated. At the bottom of its housing is a built-in electric heater. A schematic simplified diagram of the reactor is shown in Fig. 7, where it is indicated (the designation corresponds to the designations in Figs. 1-6): 1 - electric heater; 2 - reactor-mixer; 4 - reactor with a catalyst for producing atomic hydrogen. The feedstock was poured into the reactor-mixer 2 and heated by electric heater 1. In these experiments, to reach the cracking stage, the temperature of the feedstock was predominantly up to 430-470 ° C, although some heavy media such as tar had to be heated above the specified temperature, pressure up to 1 MPa. Molecular hydrogen is supplied from the cylinder (with a larger

pressure than the pressure in the reactor-mixer, so that the feed does not enter the reactor with the catalyst) in the reactor 4 with the nickel, molybdenum or platinum catalyst in it (in the form of granules with a diameter of 1-3 mm). Hydrogen and a reactor with a catalyst 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 flat cylinder (with a diameter of 85 millimeters and a height of 75 millimeters), into which the catalyst is placed, mounted horizontally in the cross section of the mixer reactor, with a hydrogen supply pipe for the distribution of hydrogen over the cross section of the reactor and distributed over the entire upper the plane of the reactor with holes with a diameter of 0.1 mm for the distribution of the resulting atomic hydrogen over the cross section of the reactor-mixer. The design of the reactor with the catalyst can be double-sided, spherical, etc., this is not of fundamental importance. Atomic hydrogen generated in a reactor with a catalyst is distributed over the entire cross section of the mixer reactor and enters directly into the cracking zone of the feedstock, where the saturation reaction of open radical bonds takes place. Light reaction fractions are discharged through the upper nozzle with a valve from the reactor-mixer, cooled and analyzed. The heavy separation residue remains in the mixing reactor and is also analyzed at the end of the experiment. The mixing reactor is equipped with thermocouples for measuring temperature and a manometer for measuring pressure. In this embodiment, the stages of heating and cracking the raw materials, heating and cracking the separation residue, heating hydrogen or hydrogen-containing media and a catalyst, producing active atomic hydrogen, mixing the cracked raw material with active hydrogen and separating the reacted light portion and the heavy residue are combined in one apparatus. Some results obtained at the laboratory facility are shown in Table 1. The processing depth reaches 87%, and the sulfur content decreased by almost 10 times. With the addition of 5% shale crushed to oil sizes of 0.05-2 micrometer in the mixing reactor reactor, the yield of light target fractions increased to 89%, i.e. part of the solid hydrocarbons was processed into light liquid hydrocarbons. With repeated processing, the yield of the target fractions will increase to almost 100%. To achieve almost the same results in this utility model, instead of hydrogen, you can use a propane-butane mixture from a balloon and other light products enriched with hydrogen or fractions. This approach is not a prototype of the industrial process, but makes it easy to demonstrate the specific implementation of the proposed utility model.

Table 1 Selection limits The output of fractions for oil,% of the mass. Source oil Reaction products The beginning of the boil, ° C 79 46 up to 200 ° C 10.6 38,4 up to 250 ° C 15.1 47.9 up to 300 ° C 22.2 71.2 up to 360 ° С 29.9 87.2 The sulfur content,% of the mass. up to 5.0 up to 0.6

In conditions as close as possible to industrial, the proposed utility model is implemented on a bench installation with a capacity of up to 30 kg / h. A step-by-step diagram of the bench installation is shown in figure 1. The installation is equipped with various capacitive equipment for storing raw materials and collecting the resulting products, heat exchange equipment for heating raw materials and the remainder of the separation and cooling of products, pumping equipment and instrumentation. Raw materials are pumped into the coil of an electric heater 1 (analogous to an industrial furnace), then the heated raw materials are supplied to the mixer reactor 2. The hydrogen from the cylinder is heated (Fig. 1, position 3), passed through a heated reactor with catalyst 4, and also fed into the reactor -mixer (figure 1, position 2), the reacted mixture is sent to the separation unit 5, for example, dispersed with decreasing pressure in the capacitive apparatus. In this embodiment, block 2 (reactor-mixer) and block 5 (separator) can be combined in one apparatus. Simultaneously with or in front of the dispersion, in order to initiate cracking, it is advisable to expose the product stream sequentially or simultaneously to cavitation, sound, and ultrasonic action created by the movement of the stream, moreover, a mixture of hydrocarbons can be exposed to this effect repeatedly and active hydrogen is supplied to cavitation, sound, and ultrasonic devices 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 through 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, by direct mixing and further joint movement with high speeds along the channels from obstacles of various shapes and curvatures. In addition, hydrogen or hydrogen-containing fractions and a reactor with a catalyst for producing atomic hydrogen can be heated due to the temperature of the raw materials and the separation residue, therefore, the blocks for heating and cracking raw materials, heating hydrogen or hydrogen-containing media and a catalyst, producing active atomic hydrogen, mixing cracked raw materials with active hydrogen and separation into the light part and the heavy residue can be combined in one device.

The process is continuous. Some results obtained at the bench installation for the implementation of the proposed utility model are shown in table 2. The processing depth reaches 96%. Taking into account the generated non-condensed gases, one can confidently talk about 100% depth of processing of raw materials using this utility model.

table 2 Selection limits The output of fractions for oil,% of the mass. Source oil Reaction products The beginning of the boil, ° C 79 39 up to 200 ° C 10.6 41.2 up to 250 ° C 15.1 49.6 up to 300 ° C 22.2 78.1 up to 360 ° С 29.9 96.3 The sulfur content,% of the mass. up to 5.0 up to 0.1

Thus, the technical result is an increase in the yield of light target intermediates or fractions (gas, gasoline, kerosene and diesel, as well as fractions for petrochemical and chemical industries) to 100% and, accordingly, an increase in the processing depth to 100%, an improvement in the quality of the obtained fractions for their further transportation and processing with a simultaneous reduction in operating and capital costs - this is achieved by organizing the preparation process in which the raw materials and the catalyst do not contact, as a result of which atalizator not poisoned by harmful impurities and coke, which leads to an increase in catalyst durability and eliminating the need of regeneration processes, the processing recess to 100% can be achieved by this utility model due to retransmission possibly multiple, handling heavy residue separating the reaction products.

Claims (5)

1. Scheme for the preparation and in-depth processing of hydrocarbon feedstocks, including blocks for purifying raw materials from harmful impurities, heating the feedstock and hydrogen and feeding them to a reactor with a catalyst, as well as production units for commercial products, characterized in that it is liquid (for example, oil, oil residues and other) the feedstock after the block from harmful impurities is sent to the heating block or to the heating block and thermal and / or thermomechanical cracking and fed to the reactor-mixer without catalyst, molecular hydrogen or light hydrogen-containing hydrogen-enriched media, for example, natural or associated gas, in particular gas and light shoulder straps of gasoline fractions obtained in the preparation process, if necessary, are heated separately from the raw materials in the heating block of hydrogen or hydrogen-containing media, sent at a higher pressure than the pressure in the reactor -mixer, to obtain active atomic hydrogen in a reactor with a catalyst heated to the required temperature, after which the active hydrogen is sent to the mixing reactor in the cracking zone for intensive mixing to raw materials and active hydrogen for the reaction, the reaction products after the mixing reactor are sent to the separation unit, light target reaction fractions with a boiling point of up to 360 ° С are mainly sent to the target product unit such as liquefied gas, gasoline, kerosene, diesel fuel , petrochemical products, etc. to the place of preparation and processing of raw materials according to this utility model or transported to a remote place for the receipt of light commercial products, the heavy residue after the stage section predominantly with a boiling point of 360 ° C partially or completely sent to the block for the production of heavy commercial products such as bitumen, coke, etc. and / or partially or completely sent for re-processing according to this utility model to the beginning of the process together with the feedstock or separately to the next stage of processing, solid hydrocarbons (for example, coal, shale, vegetable products, etc.) are sent to the fine grinding unit and introduced into the feedstock and / or heavy separation residue before it by reprocessing, gaseous hydrocarbons are also introduced into the feedstock and / or separation residue prior to reprocessing, the blocks of heating and cracking the feedstock, heating hydrogen or hydrogen-containing media and a catalyst, producing active atomic hydrogen, mixing the cracked feedstock with active hydrogen and light separation part and heavy residue can be combined in one unit. 2. The circuit according to claim 1, characterized in that the heating of hydrogen or hydrogen-containing media and a catalyst in the unit for producing active atomic hydrogen is carried out due to the heat of the heated feedstock and / or separation residue. 3. The scheme according to claim 1, characterized in that the production of atomic active hydrogen is carried out using a 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. 4. The scheme according to claim 1, characterized in that gaseous hydrocarbons are used as the feedstock, and gaseous hydrocarbons can be used as heat and mass carrier in the processing of solid hydrocarbons in the form of fine powders. 5. The scheme according to claim 1, characterized in that the separation residue before reprocessing is subjected to purification from harmful impurities and compounds, in particular from inorganic ones.