RU2503709C1 - Processing method of oil and/or oil residues - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: invention refers to a processing method of oil and/or oil residues, which involves plasma chemical pyrolysis of homogenised mixture representing a three-phase system homogeneously dispersed in hydrocarbon raw material, obtained in a plasma disperser, consisting of high-disperse particles of catalyst, methane-hydrogen fraction extracted at the separation stage of hydrocarbon pyrolysis products, and gasoline fraction extracted at the separation stage of hydrocarbon pyrolysis products, tempering, extraction of technical carbon and solid particles of waste catalyst by filtration and a separation stage of hydrocarbon pyrolysis products so that methane-hydrogen fraction and gasoline fraction are obtained and recycling of some part of methane-hydrogen fraction and gasoline fraction to a plasma disperser, and then, to a stage of plasma chemical pyrolysis. As a catalyst, high-disperse particles of concentrate of metal compounds are used, which is obtained at plasma chemical pyrolysis of oil or oil residues in mixed methane-hydrogen plasma.

EFFECT: simpler method owing to using more active high-disperse catalyst.

2 cl, 3 ex

Description

The present invention is applicable in the petrochemical and chemical industries, specifically in the technology of oil refining, heavy oil residues, as well as gas condensates and natural gas.

Classical methods of thermocatalytic refining of oil and oil fractions are known [Handbook of petrochemistry. t. 1. / Ed. Ogorodnikov S.K. - L .: Chemistry,] in which they carry out:

- atmospheric distillation of oil to produce gasoline, kerosene, diesel fractions and fuel oil;

- vacuum distillation of fuel oil to obtain vacuum gas oil or oil distillates;

- catalytic cracking of vacuum gas oil to produce gasoline;

- hydrocracking of a diesel fraction with purification from hydrogen sulfide;

- catalytic reforming of gasoline fractions to produce high octane gasoline;

- thermal pyrolysis of liquefied gases (ethane, propane and butane fractions) and low-octane gasoline to produce ethylene, propylene and acetylene.

The disadvantages of the mentioned classical schemes include the low depth of oil refining and oil fractions into motor fuel (not more than 65%) and unsaturated hydrocarbons (not more than 45% of the mass of raw materials). In particular, thermal pyrolysis has the following disadvantages:

- great dependence on the quality composition of raw materials;

- multi-stage and branching processes leads to a decrease in manageability and quality, as well as an increase in losses;

- a large number of resins is formed, and with a heavier feedstock, for example, when switching from ethane to diesel fractions, the resin yield doubles;

- the transition to high-boiling fractions (kerosene and diesel) is associated with a decrease in ethylene yield and increased coking of the furnace coils.

At present, a critical situation has arisen in the world with the utilization of oily waste, the elimination of sludge and sludge storage tanks, and the cleaning of land contaminated with oil products.

Liquid wastes containing more than 14% of petroleum products are mainly burnt. The most promising use of a fuel-oil emulsion as a fuel. When the oil content in the waste is less than 14%, microbiological treatment methods are used. However, until now, an acceptable solution to the most difficult problem has not been found - cleaning the land, repeatedly contaminated with oil products (for example, the soil of the territories of service stations, seaports, railway depots, oil depots, etc.), as well as the disposal of bottom sediments of oil tanks, settling ponds, earthen slurry barns, which are a solid phase containing paraffins, asphalt-resinous substances, sulfur, sand, clay and other mechanical impurities, as well as heavy metals - lead, cadmium, zinc, etc.

In existing practice, it is proposed to process such waste in thermal decontamination plants, where pyrolysis produces dry neutralized carbon-containing material - raw materials for the production of building materials and asphalt mixtures, as well as condensate and gas used as fuel in the installation itself. This solution to the problem is not satisfactory, since the solid pyrolysis residues contain heavy metals and, therefore, are not suitable for industrial use and require disposal.

Extraction of oil from bottom sediments is impractical due to high costs and a small amount of the oil phase: an average of 5-8%.

Utilization of acid tars - waste of sulfuric acid purification of some petroleum products, for example, lubricating oils - is a problem for many governments. Tars are dangerous because they contain resinous substances, organics, heavy metals, sulfur, products of polymerization of unsaturated hydrocarbons, and the presence of sulfuric acid dissolved in water reaches 70%. No less dangerous for the environment is the method of storing tar in open pits for this purpose, which then turn into tar lakes, the water layer in which is actually only 0.3-0.4 m, and then 7-8 m deeper - fuel oil-like mass. Most of the disposal methods come down to regeneration of sulfuric acid from acid tars and burning of neutralized residues or to neutralization with limestone, followed by burning at thermal power plants. As a result, highly toxic substances are released into the atmosphere, which is completely unacceptable in modern conditions.

The most rational way to solve the problem of the disposal of oily waste and / or heavy oil fractions is a joint pyrolysis process with municipal solid waste. The correctness of the economic feasibility of such a technology is confirmed by the introduction of several plants that provide for the joint utilization of oil-containing, rubber-fabric, textile wastes, oiled rags, sawdust, wastes of paints and varnishes, polymer films, etc. However, however, issues related to environmental protection have not been resolved either. environment from pollution by heavy metals, dioxins, furans.

Currently in the world practice there are several technologies for the joint thermal processing of municipal solid waste and silt sludge from wastewater generated in urban wastewater treatment plants. At the same time, they are planned to be co-incinerated in furnaces of various designs with preliminary drying of precipitation and mandatory return of flue gases after drying for deodorization in the furnace. Due to the high content of heavy metals in the sludge of sewage, all these technologies lead to the production of extremely dangerous slag and ash, which require disposal. In addition, organochlorine compounds contained in solid waste lead to environmental pollution by dioxins, furans and biphenyls, which are extremely dangerous for human health and the environment as a whole.

The most promising at present is the technology of co-processing of oily waste and / or heavy oil fractions with municipal solid waste using plasma processing technologies using low-temperature plasma (2000-10000 ° C).

Plasma-chemical methods provide a higher degree of processing (conversion of raw materials is 96-98% of the mass), increase the processing depth to unsaturated hydrocarbons (more than 75%), allow the use of heavy oil fractions (kerosene and diesel) as raw materials, and also reduce the number of stages and reduce branching of chemical processes.

The processes of plasma-chemical processing of hydrocarbon feedstocks, including oily waste and / or heavy oil fractions, can be classified according to the following main features:

1) the phase state of the raw materials subjected to plasma-chemical processing:

a) gaseous hydrocarbons or mixtures thereof;

b) liquid hydrocarbons or mixtures thereof;

c) solid hydrocarbon feedstocks;

d) a mixture of liquid and solid hydrocarbons;

e) a mixture of gaseous, liquid and solid hydrocarbons;

2) plasma-forming gas ("working medium" of the plasma torch):

a) oxygen-containing gas, including air;

b) water vapor;

c) gaseous hydrocarbons;

d) hydrogen or hydrogen-containing gases;

e) inert gases;

f) other gases, including mixtures of the above gases;

3) the presence or absence of a catalyst:

a) without catalyst;

b) using a catalyst.

In accordance with this classification, the following is a description of the main methods for plasma processing of hydrocarbon feedstocks of various phase composition. The emphasis is on the processing of oily waste, heavy oil fractions and plasma-catalytic processes for the processing of hydrocarbon feedstocks.

Plasma-chemical processing of gaseous hydrocarbons

1a-2g-3a. Acetylene-containing pyrogas is obtained by plasma pyrolysis of natural gas under the influence of hydrogen plasma [RF Patent 2169755 C1 IPC C10G 15/12 of 12/12/1999]. Acetylene without hydrogen evolution from pyrogas is hydrogenated to ethylene in the presence of a catalyst in a liquid solvent medium (three-phase catalyst system). Ethylene is isolated from hydrogenation products by low-temperature distillation. The hydrogen-containing gas formed during the pyrolysis is returned to the pyrolysis stage, and an excess amount is used in the gas turbine unit. A small amount of liquid hydrogenation products of acetylene is also returned to the pyrolysis stage as secondary raw materials.

1a-2e-3a. In another method of plasmachemical pyrolysis of gaseous hydrocarbons, the plasma-forming gas is a mixture of gaseous hydrocarbons and pyrogas (after hydrogen and acetylene are separated from the latter) [RF Patent 2202593 C2 IPC C10G 15/12, 05.22.2001].

1a-2d-3a. A known method of plasma processing of gas hydrocarbon feedstocks (associated petroleum gases, gas condensate and other hydrocarbons) [RF Patent 2190659 IPC C10G 15/12 05/19/2000] in solid-phase products. Hydrocarbon feeds are subjected to plasma-chemical pyrolysis and plasma polymerization, solid-state polymerization products are removed from the gas-plasma stream, the unreacted hydrocarbon gas stream is purified from the gas stream, the remaining hydrogen gas is compressed, and the gas is returned as a plasma jet to the plasma-chemical hydrocarbon pyrolysis hydrocarbon feed, while solid-phase gas polymers are removed from a two-phase stream. As a plasma-forming gas, an inert gas or a mixture of gases is used, the flow rate and composition of which is selected based on measurements of the chemical composition and flow rate of hydrocarbon materials carried out before pyrolysis, according to radiation spectra and energies of electronically excited particles. The plasma and the processed hydrocarbon feed are blown into the reaction chamber in the form of subsonic jets with a controlled gas-plasma flow rate. The method provides a high degree of processing of gas hydrocarbon feedstocks into solid-phase hydrocarbon polymers, including cross-linked ones.

1a-2g-3a. In the method of producing ethylene, acetylene and other lower olefins from methane [RF Patent 2158747 IPC C10G 15/12 03/21/2000] natural gas is preheated to 900-1000 K, and methane conversion is carried out in two stages, in the first of which the gas is heated to 1800-2100 K in a time of 1-2 ms, at the second stage, the heated mixture of the products of the primary transformation is maintained at a pressure of 2 5 MPa in adiabatic mode for 5-10 ms. Next, the reaction products are quenched. Moreover, the above temperature range at the first stage of methane conversion is maintained by supplying energy from the outside. The pyrolyzable mixture is heated in the first stage in a plasma stream of hydrogen. The method allows for the direct conversion of methane and to obtain 67.4% of ethylene and 9.1% of acetylene in the pyrolysis products with a methane conversion of 88.4%.

1a-2b-3a. In the method for producing acetylene by plasma-chemical pyrolysis of hydrocarbons [RF Patent 2078117 IPC C10G 15/12 12/29/1993] water vapor is introduced into the plasma-forming gas of the plasma-chemical pyrolysis of hydrocarbons. The molar ratio of carbon to oxygen in the mixture is 1: (1-1.5), preferably 1: 1.1. Carbon tail gases are used as the plasma forming gas. For the formation of water vapor and / or cooling the reaction products, water saturated with hydrocarbons is used.

Plasma-chemical processing of liquid hydrocarbons

1b-2v-3a. In the method [RF Patent 2026334 IPC C10G 15/12 01/09/1995] gas condensate is processed in a plasma jet of gas condensate. The resulting products are quenched with liquefied hydrocarbon with simultaneous throttling and re-quenched with liquefied hydrocarbon.

1b-2g-3a. A known method of producing acetylene and ethylene from hydrocarbons using plasma-chemical reactions [Krapivina S.A. Plasma-chemical technological processes. - L .: Chemistry, 1981. - c. 182]. According to this method, liquid hydrocarbons are sequentially subjected to plasma-chemical pyrolysis in a plasma-forming gas (industrial hydrogen or a mixture of hydrogen with methane, the soot and tar are purified from the pyrogas, pyrogas are compressed and dried, and finally the latter is separated from hydrocarbons of the form C ₃ , C ₄ and higher ( acetylene homologues).

Plasma-chemical processing of heavy oil residues

1v-2g-3a. In the method [RF Patent 2131906 IPC C10G 15/12 01/27/1997] processing heavy resins containing emulsion water and coke, use is made of plasma-chemical pyrolysis with subsequent quenching of the products and their separation. The raw materials are pre-homogenized, the pyrolysis products after quenching are purified from acetylene by catalytic hydrogenation, condensed and sent to the main production, the condensate is returned to the hydrogenation of acetylene, its excess is mixed with the raw material, and the methane-hydrogen fraction after separation is used as a plasma-forming gas and / or boiler fuel . The method allows to organize the transition to a low-waste closed-loop system of complex processing of raw materials through the disposal of environmentally hazardous waste from the petrochemical and chemical industries, as well as to increase the degree of use of raw materials and the yield of the final product.

1v-2g-3a. In the method of [RF Patent 2129584 IPC C10G 15/12 07/19/1996], heavy oil residues are subjected to plasma-chemical pyrolysis in a stream of hydrogen-containing gas to produce pyrogas, carbon black and transfer sulfur compounds to hydrogen sulfide. The pyrolysis products are purified from carbon black, followed by the precipitation of rare metals by known methods, hydrogen sulfide is subjected to dissociation in a microwave plasma to obtain polymer sulfur and hydrogen, returning the latter to the pyrolysis stage. Motor fuel is synthesized from purified gases. The method allows to expand the raw material base, increase the efficiency of the processing process and increase the degree of use of raw materials.

1v-2g-3a. A known method of hydrocracking of heavy hydrocarbon fractions [RF Patent 2319730 IPC C10G 15/12 11/09/2006]. The heavy hydrocarbon fraction preheated to 60-370 ° C is subjected to “bombardment” with hydrogen ions and hydroxyl group ions in the reactor without oxygen, while hydrogen ions and hydroxyl group ions are supplied to the chamber as a plasma. The method is implemented in a device for hydrocracking of heavy hydrocarbon fractions, comprising a reactor having a level sensor, a temperature sensor, an outlet pipe for the unreacted part of the hydrocarbon fractions in the vapor state. A plasmatron is installed in the upper part of the reactor with a nozzle, and in its lower part a nozzle for supplying heavy hydrocarbon fractions with a nozzle installed with the possibility of controlling the distance from the plasma torch nozzle to its upper part. The method and device for its implementation are aimed at simplifying the technology of hydrocracking of heavy hydrocarbon feedstocks, increasing productivity due to the possibility of controlling the degree of fragmentation of hydrocarbon molecules by the time of "bombardment" of their ions, the kinetic energy of ions, the initial temperature of hydrocarbon molecules, as well as the ability to operate the device in two technological modes : receiving gas or liquid light fractions.

1c-2e-3a. Hydrocracking using plasma technologies is described in the method [RF Patent 2343181 IPC C10G 15/12 10/17/2007]. The heavy hydrocarbon fraction preheated to 60-350 ° C is subjected to plasma to break down hydrocarbon molecules into atoms in the high-temperature zone without oxygen, followed by their “bombardment” of other hydrocarbon chains, their fragmentation and hydrogenation in the reaction zone, leading to the formation of light hydrocarbon fractions. Plasma is an ionized high temperature gas.

1v-2d-3a. In the work [Kashapov N.F., Nefedev E.S., Timerkaev B.A., Fakhrutdinov I.M. Decomposition of heavy hydrocarbons by electric arc plasma. The 36th International (Zvenigorod) Conference on Plasma Physics and TCB, 2009, p.1] we are talking about the processing of highly viscous oil residues - fuel oil and tar. It is emphasized that in recent years, as one of the options for deepening the processing of heavy oils and fuel oil, it is proposed to use a powerful destructive pyrolysis process in a plasma jet of inert gas, hydrogen-containing gas, nitrogen, which has unique capabilities both in terms of the selectivity of chemical reactions and the ease of implementation of technological process. The intensities of chemical reactions depend on many factors, the main ones of which are gas and raw material temperatures, molar ratios between the coolant and raw materials, state of molecular excitations, reaction rates, heat and mass transfer of gas dynamics, electrodynamics, etc. A kinetic description of plasma-chemical technological processes allows us to trace their development in time taking into account temperature, pressure, type of feedstock. The studies were carried out in a plasma generator with longitudinal blowing of the arc and with vortex stabilization of the arc. Oil heated to 80 ° C was fed into the zone of plasma exit from the anode. Gas heating in an electric arc occurred mainly due to the energy released in the arc column. Mixed with a plasma-forming gas, the reacting mass passed through the reaction chamber and entered the quenching chamber. After the quenching chamber, the processed product fell into the chamber with a large volume, where it was leveled by the distribution of composition and speed and passed through the zone of final cooling. At the outlet, the gaseous product of processing had a temperature of 25-30 ° C. The final product was composed of gas and solid phases. The solid phase was fine soot. The formation of light hydrocarbon fractions due to thermal decomposition of heavy fractions is possible at temperatures below 1000 K. Therefore, in an electric arc plasma with a temperature of 3000-6000 K, hydrocarbons with a carbon bond of the type C ₂ H ₂ , C ₂ H ₄ , C ₄ N are mainly formed ₄ , as well as molecular hydrogen and atomic carbon.

Plasma-chemical processing of solid or a mixture of solid and liquid raw materials

1g-2e-3a. A known method of producing acetylene by pyrolysis of crushed solid raw materials, previously mixed with water vapor, in a pulsating jet of plasma pulsating for 0.001-0.009 [RF Patent 2009112 IPC C10G 15/12 06/05/1992]. Organic waste is used as raw material.

1g-2g-3a. A known method of processing and disposal of bottom sediments of oil sludge pits [RF Patent 2201407 IPC C10G 15/12 10/30/2001]. The method includes plasma-chemical treatment of bottom sediments in the presence of hydrogen, preheated to a temperature of 3000-4000 ° C, to obtain unsaturated hydrocarbons C ₂ -C ₄ . Before plasma-chemical treatment, the bottom sediments of oil sludge pits are diluted with crude oil in a mass ratio of 1: 0.25 and heated to a temperature of 90-95 ° C. The technical result is the creation of a small-sized, high-performance, inertia-free, environmentally friendly technology for processing waste from bottom sediments of oil sludge pits to obtain target products.

1g-2b-3a. The method of gasification of solid carbonaceous materials [RF Patent 2213766 IPC C10G 15/12 17/06/2002] provides for the production of synthesis gas from plastic waste and includes the supply of dispersed raw materials, water vapor plasma, their mixing, subsequent plasma-thermal gasification of the raw materials and removal of the resulting products. In the method, a two-phase flow of dispersed feed and water plasma is directed to a bath of melt formed by melting the unreacted portion of the particulate feed. The obtained gasification products are diverted in countercurrent to the initial two-phase stream and mixed with the subsequent formation of a swirling stream. The method is implemented in a device containing a plasma thermal reactor, two-jet plasmatron, nodes for the controlled input of dispersed raw materials and water vapor, nodes for the output of synthesis gas and solid particles. Plasma-thermal reactor consists of plasma and cyclone reactors connected by a gas duct. The method allows to increase the economic efficiency of the plasma-thermal process for producing high-quality synthesis gas in a compact plasma-thermal reactor in one technological stage.

Plasma-catalytic processing of hydrocarbons

1b-2g-3b. In the method of purification of oil fractions from organosulfur compounds [RF Patent 2144558 IPC C10G 15/12 05/13/1997], including high-temperature pyrolysis in the presence of hydrogen and a catalyst, the process is carried out in a plasma-chemical reactor, with a part of the catalyst dispersed in the feed by the mechanochemical method, and the other part of the catalyst served in the hardening device of the reactor in the form of a suspension. The method allows for deep purification of oil fractions and reduce the amount of harmful waste.

1v-2e-3b. A known method of disposal of oil sludge [RF Patent 2218378 IPC C10G 15/12 12/12/2002] by plasma treatment of oil sludge in the presence of catalysts. Plasma treatment of oil sludge is carried out in the form of dispersed combustible water-fuel compositions under the conditions of a catalytically active air plasma of electric discharges at a mass average temperature of 1500-6000 K for 10 ^-5 -10 ^-3 s with a content of ultrafine catalytically active materials of 0.01 - 1.0 mass. % obtained in the process of plasma-catalytic disposal of oil sludge Plasma-catalytic reactor contains a plasma generator, a reaction chamber, a nozzle and nozzles for the input of raw materials and output of products, and plasma the herator, the reaction chamber and the disk nozzle are located horizontally on the same axial line, the plasma generator and the disk nozzle are connected to the reaction chamber from opposite sides, the disk nozzle contains a drive shaft on which an external chamber with emulsifier disks and an inner chamber containing a sleeve with holes are mounted and a dispersant disk, interconnected by a housing with a sealing ring located on it, and the reaction chamber contains a quartz tube and a water-cooled housing located the outlet pipe for disposal products displayed on it. The advantages of the installation and method include: small dimensions, compactness and mobility of the installation, high specific productivity of the installation, low specific costs of electricity for utilization, obtaining additional thermal energy from utilization for technological and domestic needs, low content of pollutants in the purified exhaust gases of the installation, lack of polluting organic substances in solid waste products, lack of discharge of contaminated water.

1a-2d-3b. Obtaining ethylene in the method [RF Patent 2315802 IPC C10G 15/12 01/28/2004] provides for the conversion of methane by plasma-catalytic oxidation. The method includes activation of the catalyst by microwave radiation and the formation of a nonequilibrium "cold" microwave plasma. At the same time, the catalyst is activated by microwave radiation and microwave plasma and creates a nonequilibrium "cold" microwave plasma.

1a-2g-3b. The combination of the plasma chemical and catalytic pyrolysis processes is implemented in the method of producing acetylene from natural gas [Khudyakov G.N. et al. Effect of activating additives on the plasma-chemical process of the formation of acetylene from natural gas. / II All-Union Symposium on Plasma Chemistry. - Abstracts. - Riga: Zinatne, 1975. - p.243-246]. In this method, an activating additive (potassium carbonate powder) is fed from the feeder into the plasma stream of hydrogen, the stream is mixed with jets of natural gas and the pyrolysis reaction is carried out, and then the reaction products are cooled. This method allows you to slightly increase the yield of the final product, but does not allow the full use of activating additives, because after the introduction of the additive, the mixture of the plasma stream with natural gas is not homogeneous enough. Thus, the intensity of the processes of plasmachemical pyrolysis is reduced, the specific energy consumption is increased, and the consumption of additives is increased.

1v-2g-3b. A known method of processing oil and oil residues [RF Patent 2149885 IPC C10G 15/12 04/22/1997]. In accordance with this method, plasmachemical pyrolysis of oil and oil residues is carried out in the presence of a catalyst, quenching of the pyrolysis products and separation of the pyrolysis products. A finely dispersed catalyst is used, which, regardless of the phase state (solid, liquid or gaseous), is preliminarily dispersed homogeneously with the feed, and then the resulting mixture is subjected to plasma-chemical pyrolysis. The weight of the catalyst is preferably 1-5% by weight of the feed. The used catalyst after separation of the pyrolysis products is regenerated and returned to the pyrolysis step. The process consists of the stage of preparing the feedstock and catalyst, in which the feedstock is mixed with a finely divided catalyst, the mixture is homogenized and sent to the next stage, where the homogenized mixture is subjected to plasma-chemical pyrolysis to obtain pyrolysis products that are sent to the separation stage. When separating the products of pyrolysis, the catalyst is regenerated and returned to the stage of preparation of raw materials, and carbon black is collected for further use. The pyrocondensate is separated into unsaturated C ₂ -C ₄ hydrocarbons, gasoline and hydrogen methane fractions, returning the latter to the stage of plasma chemical pyrolysis.

The disadvantage of this method is the complexity of the process along the catalyst circuit, associated with the need for mandatory allocation of the catalyst and its reuse in the process.

The aim of the present invention is to simplify the process technology in terms of the use of the catalyst and the intensification of the process through the use of a more active catalyst.

In accordance with the present invention, the goal is achieved by a method of processing oil and / or oil residues, including plasma-chemical pyrolysis of a homogenized mixture, which is a three-phase system homogeneously dispersed in a hydrocarbon feed obtained in a plasma dispersant, consisting of highly dispersed catalyst particles, a methane-hydrogen fraction separated in the stage for the separation of hydrocarbon products of pyrolysis, and the gasoline fraction isolated at the stage of separation of hydrocarbon products pyrolysis, quenching, separation of carbon black and solid particles of spent catalyst by filtration, and the stage of separation of hydrocarbon pyrolysis products to obtain a methane-hydrogen fraction and a gasoline fraction and recycle part of the methane-hydrogen fraction and part of the gasoline fraction into a plasma dispersant and, then, to the plasma chemical pyrolysis stage, as a catalyst, fine particles of a concentrate of metal compounds obtained by plasma-chemical pyrolysis of oil or oil wastes are used Tatka in mixed methane-hydrogen plasma.

Preferably, finely dispersed catalyst particles are used that have been processed in a medium of low-temperature plasma formed in the interelectrode space at a voltage between electrodes of 1.5-5.5 kV and a frequency of 0.25-0.8 MHz, in the presence of bubbles of methane-hydrogen mixture having a size of 0 , 1-0.5 mm and in the presence of solid parts of the starting catalyst having a size of 10-100 microns.

The process is carried out as follows. Raw materials (oil and / or oil residues) are fed to the tank. A three-phase system is presented there, which is a highly dispersed catalyst, a hydrogen-containing gas, for example, a methane-hydrogen fraction isolated at the stage of separation of hydrocarbon pyrolysis products, and a hydrocarbon fraction, for example, a gasoline fraction isolated at the stage of separation of hydrocarbon pyrolysis products.

The three-phase system is obtained in a plasma disperser, which is a closed volume in which horizontal electrodes are located, to which an electric current with a voltage of 1.5-5.5 kV and a frequency of 0.25-0.8 MHz is supplied. Large metal particles (0.1-0.5 mm), a methane-hydrogen mixture in the form of bubbles of 10-100 microns in size and a liquid hydrocarbon phase (for example, gasoline fraction) are fed into the plasma dispersant. The formation of particles of a highly dispersed catalyst occurs as a result of the occurrence of an electric discharge between horizontal electrodes and large metal particles. Mixing in the plasma dispersant occurs due to the circulation of a three-phase flow in the circulation circuit of the plasma dispersant.

From the tank, the raw materials together with the three-phase system are sent to the homogenizer (high-speed mixing device) with additional mixing using a circulation pump in the tank-homogenizer-tank circulation loop.

From the homogenizer, with the help of a dispenser, the homogenized mixture enters a plasma reactor having at least one plasmatron, the working gas of which is a methane-hydrogen mixture obtained during the process of plasma chemical pyrolysis.

The solid pyrolysis products from the plasma reactor are sent for disposal or for processing for further use as a catalyst or as a component of building materials.

The gaseous pyrolysis products from the plasma reactor are sent to a quenching device, where a sharp decrease in temperature occurs and most of the reactions, mainly radical chain reactions, cease. From the quenching device, the pyrolysis products are sent to a filter (for example, a bag filter), where carbon black and other solid particles, including spent catalyst particles, are separated. In the case when the process of plasma-chemical pyrolysis is combined with the processing of solid waste, the solid products isolated at the filtering stage are sent to the plasma reactor, mixing them with the solid waste.

After the filtration stage, the pyrocondensate is sent to the separation stage, where C ₂ -C ₄ unsaturated hydrocarbons, a gasoline fraction, part of which is sent to the plasma dispersant to obtain a three-phase system, and a methane-hydrogen fraction, part of which are sent to the plasma dispersant to obtain a three-phase system, are separated from it. The resulting three-phase system is mixed with raw materials (oil and / or oil residues), the resulting mixture after homogenization is subjected to plasmachemical pyrolysis.

The advantage of the proposed method is the use of a more active highly dispersed catalyst and a significant simplification of the process technology, eliminating the stage of separation of the catalyst and its reuse in the process. The high activity of the catalyst is associated with its production in a stream of low-temperature plasma (electrical discharge between the electrodes), as a result of which the catalyst is activated.

The invention is illustrated by examples of alternative embodiments.

Example 1

The process was carried out as follows. Oil sludge with an average flow rate of 200 kg / h was fed into the tank from the slime accumulator. A three-phase system was introduced there, which was a homogenized mixture of a finely dispersed catalyst, a methane-hydrogen fraction isolated at the stage of separation of hydrocarbon pyrolysis products, and a gasoline fraction isolated at the stage of separation of hydrocarbon pyrolysis products. The average consumption of the three-phase system was 40 kg / h, while the three-phase system contained, on average, 6 wt.% Highly dispersed catalyst, 31 wt.% Methane-hydrogen fraction and 63 wt.% Gasoline fraction.

The three-phase system was obtained in a plasma disperser, which is a closed volume in which there are horizontal electrodes to which an electric current with a voltage of 3.5 kV and a frequency of 0.8 MHz is supplied. Large — 0.1–0.5 mm — particles of the concentrate of metal compounds obtained by plasma-chemical pyrolysis of oil sludge in mixed methane-hydrogen plasma, a methane-hydrogen fraction in the form of bubbles of 10-100 microns in size and a gasoline fraction were fed into the plasma dispersant. The average consumption of the concentrate of metal compounds amounted to 2.4 kg / h, methane-hydrogen fraction - 12.4 kg / h, gasoline fraction - 25.2 kg / h. Mixing in the plasma dispersant was ensured by the circulation of a three-phase flow in the circulation circuit of the plasma dispersant. The concentrate of metal compounds obtained by plasma-chemical pyrolysis of oil sludge in a mixed methane-hydrogen plasma, according to X-ray fluorescence analysis, contained iron, nickel, cobalt, chromium, manganese, molybdenum, vanadium, and also the oxides and carbides of these metals, while the content of iron compounds in the concentrate exceeded the content of compounds of other metals.

From the tank, oil sludge together with a three-phase system was sent to a homogenizer. The homogenized mixture was fed to a plasma reactor. In the reactor, the mixture was treated for 10 ^-3 s with methane-hydrogen plasma obtained using an EDP-200 plasmatron (Research Center Kurchatov Institute) with a power of 200 kW.

The gaseous pyrolysis products from the plasma reactor were cooled in a quenching device, from the quenching device, the pyrolysis products were sent to a bag filter where carbon black and other solid particles, including spent catalyst particles, were separated. After pyrolysis, an average of 9 kg / solid pyrolysis products were isolated.

After the filtration stage, the pyro-condensate was sent to the separation stage, where unsaturated C2-C4 hydrocarbons, gasoline fraction and methane-hydrogen fraction were separated from it. After pyrolysis, an average of 152 kg / h of unsaturated hydrocarbons C2-C4, 38 kg / h of gasoline fraction, 41 kg / h of methane-hydrogen fraction was isolated, then 30% of the obtained methane-hydrogen fraction was sent to a plasma dispersant to obtain a three-phase system, to a plasma dispersant for Obtaining a three-phase system was also directed to 66% of the obtained gasoline fraction.

Example 2

The process was carried out analogously to example 1, while crude oil was used as a raw material, and a metal compound concentrate obtained by plasma-chemical oil pyrolysis in mixed methane-hydrogen plasma was used as a catalyst, the metal compound concentrate contained iron, nickel, cobalt, chromium, manganese, molybdenum, vanadium, as well as the oxides and carbides of these metals.

Example 3

The process was carried out analogously to example 1, with a mixture of oil and oil sludge containing 50 wt.% Oil and 50 wt.% Oil sludge being used as raw material, and a metal compound concentrate obtained by plasma-chemical pyrolysis of a mixture of oil and oil sludge was used as a catalyst in mixed methane-hydrogen plasma, the concentrate of metal compounds contained iron, nickel, cobalt, chromium, manganese, molybdenum, vanadium, as well as oxides and carbides of these metals.

Claims (2)

1. A method of processing oil and / or oil residues, including plasma-chemical pyrolysis of a homogenized mixture, which is a three-phase system homogeneously dispersed in a hydrocarbon feed, obtained in a plasma dispersant, consisting of highly dispersed catalyst particles, a methane-hydrogen fraction isolated at the stage of separation of the hydrocarbon pyrolysis products, and gasoline fraction isolated at the stage of separation of hydrocarbon products of pyrolysis, quenching, carbon black and solid particles spent catalyst by filtration and the stage of separation of hydrocarbon pyrolysis products to obtain a methane-hydrogen fraction and a gasoline fraction and recycle a part of the methane-hydrogen fraction and a part of the gasoline fraction into a plasma dispersant and, then, to the plasma-chemical pyrolysis stage, using finely dispersed metal compound concentrate particles obtained as a catalyst with plasma-chemical pyrolysis of oil or oil residues in a mixed methane-hydrogen plasma. 2. The method according to claim 1, characterized in that they use highly dispersed catalyst particles that have been processed in a medium of low-temperature plasma formed in the interelectrode space at a voltage between the electrodes of 1.5-5.5 kV and a frequency of 0.25-0.8 MHz in the presence of bubbles of methane-hydrogen mixture having a size of 0.1-0.5 mm and in the presence of solid particles of the starting catalyst having a size of 10-100 microns.