RU2794676C1 - Method for obtaining gasoline fractions and aromatic hydrocarbons - Google Patents

Abstract

FIELD: oil refining; petrochemical industry.

SUBSTANCE: method for producing gasoline fractions and aromatic hydrocarbons, in which a hydrocarbon fraction, a fraction containing one or more olefins selected from the group including ethylene, propylene, normal butylenes, isobutylene, and water are distributed evenly into a reactor filled with a zeolite catalyst and including at least two consecutive independent reaction volumes, or at least two series-connected reactors. The hydrocarbon fraction is supplied to at least the first reaction volume, the olefin-containing fraction and water are also supplied to the first reaction volume, the second and subsequent reaction volumes are supplied with a mixture of the olefin-containing fraction and water, or only water, the volumetric supply of water is carried out in the first reaction volume - from 20 to 25% of the total volume of water supplied, in the second and subsequent - the rest, so that water is supplied to each reaction volume, and the volumetric rate of water supply is adjustable. The proportions of the supplied components are 85-92.7 wt.% hydrocarbons; 3.7-7 wt.% olefin-containing fraction; 2-10 wt.% water.

EFFECT: creation of a method for the production of gasolines or concentrates of aromatic compounds by joint processing of hydrocarbon fractions and olefin-containing fractions with distributed supply to several series-connected reaction volumes with controlled water supply.

12 cl, 5 tbl, 19 ex

Description

The invention relates to the field of oil refining and petrochemical industry. More specifically, the invention relates to a method for the production of gasolines or concentrates of aromatic compounds by co-processing hydrocarbon fractions and olefin-containing fractions with a distributed supply to several series-connected reaction volumes while supplying water to the reaction volumes.

The description uses the following terms:

Gasoline - commercial gasoline or a component for the production of commercial gasoline. In particular, gasoline obtained by the proposed method can be used to produce motor gasoline by compounding methods (mixing gasoline fractions obtained by various oil refining processes). For example, the proposed method can be used to produce a basis for the production of motor gasoline of the environmental class K5 brand AI-92 according to GOST 32513-2013 (TR CU 013/2011). In some cases, the gasoline obtained by the proposed method may not meet all the requirements for commercial gasoline by a particular region or organization. For example, the content of benzene in the produced gasoline may exceed 1.0 vol. %. As another example, the content of aromatics in the produced gasoline may exceed 35 vol. %. As a component of gasoline, a liquid hydrocarbon product produced by the proposed method can be considered.

Hydrocarbon fraction - a fraction of the gasoline boiling range (the initial boiling point is not standardized, the final boiling point is not more than 215 ° C). In particular, the end of the boil may be 200°C, 180°C, 160°C or 85°C. Preferably, the end boiling point is not higher than 180°C. The onset of boiling may be, for example, 32°C, 62°C, 85°C, 140°C. Preferably, the initial boiling point is not lower than 62°C.

Olefin-containing fraction - a fraction comprising 10-90 wt. % C2-C4 olefins (ethylene, propylene, normal butylenes, isobutylene).

The olefin-containing fraction may contain inert or slightly reactive components other than olefins, for example: methane, ethane, propane, butane, isobutane, hydrogen, nitrogen. For example, the olefin-containing fraction may contain from 0.5 to 8.0 wt. % hydrogen, preferably from 0.5 to 2 wt. % hydrogen. Preferably, the mass fraction of C5+ hydrocarbons in the olefin-containing fraction is not more than 5.0 wt. %. Preferably, the volume fraction of hydrogen sulfide in the olefin-containing fraction is not more than 0.5%.

The prior art technology for producing a high-octane gasoline product by zeoforming is a process of catalytic processing of low-octane gasoline fractions (straight-run gasoline fractions of oils and gas condensates, gas gasolines and other fractions boiling away in the temperature range of 35-200 ° C) into high-octane unleaded gasolines on zeolite-containing catalysts , as well as various options for the development of this technology. For example, a method for obtaining gasoline fractions and aromatic hydrocarbons [RU 2103322, publication date 01/27/1998] describes a variation of the zeoforming technology, in which gasoline fractions and aromatic hydrocarbons are obtained by processing low-octane hydrocarbon fractions boiling in the range of 35-200 ° C on zeolite catalysts at a temperature 340-480 °C and a pressure of 0.1-2.0 MPa and a feed space velocity of 0.5-4.0 h ^{- 1} by the Zeoforming method, while the hydrocarbon feed is mixed with olefinic hydrocarbons, and / or alcohols, and / or ethers in the amount of 5...20 wt. on the amount of low-octane hydrocarbon fractions supplied to the catalyst. Or a method for the alkylation of aromatic hydrocarbons in the liquid phase [US 7449420, publication date 11/11/2008], in which for a product with boiling ranges corresponding to the gasoline fraction, from a feed stream from a mixture of light olefins, including ethylene and propylene, and a stream of liquid aromatic feedstock, containing benzene, light olefins are extracted from the flow of gaseous olefins by countercurrent dissolution in the flow of light aromatic hydrocarbons, then the aromatic hydrocarbons contained in the extract flow are alkylated with the extracted olefins dissolved in the flow of aromatic hydrocarbons on a fixed bed of a solid alkylation catalyst based on molecular a sieve containing a zeolite of the MWW family, by reaction in the liquid phase at a temperature not exceeding 250°C, then vapor-phase alkylation is carried out, on a fixed catalyst bed, including a zeolite catalyst ZSM-5, at a temperature of 200 to 325°C, and then fractionation is performed products.

The disadvantages of the methods described above include the period of operation of the catalyst before deactivation, which is usually caused by coking of the catalyst. The problems associated with the need to replace the catalyst and (or) its reactivation are due to the unevenness of the temperature field over the catalyst layer, temperature drops during the course of the reaction.

Also, other options for the development of zeoforming technology are known from the prior art, in particular, a method for producing gasolines or concentrates of aromatic compounds with different distribution of oxygenate and olefin-containing fraction flows and the addition of water [WO 2022005332, publication date 01/06/2022]. The process uses three streams as feedstock, the first of which includes a hydrocarbon fraction, the second stream includes an oxygenate, the third stream includes an olefin-containing fraction, the olefin-containing fraction comprising one or more olefins selected from the group consisting of ethylene, propylene, normal butylenes, isobutylene, in a total amount from 10 to 50 wt.%, and also in some cases, water is supplied with a fourth stream. Three reaction zones filled with zeolite catalyst are used, the first stream is fed into at least one reaction zone, the second stream is fed into the last reaction zone only, the third stream is fed into the first and second reaction zones, and water is added to the first and second reaction zones, and the product stream from the first reaction zone is fed to the second reaction zone, and the product stream from the second reaction zone is fed to the third reaction zone. The method makes it possible to reduce the content of heavy hydrocarbons in the product, to obtain a product with an end boiling point below 215°C and a resin content of less than 5 mg/100 cm ³ , to refuse from the recycle of gaseous products, and also to reduce the consumption of oxygenates. This technical solution is the closest to the claimed invention. However, the disadvantage of this method is the use of four streams at the reactor inlet, one of which is alcohol, which, unlike hydrocarbon and olefin-containing fraction streams, is not a typical product of primary oil refining processes, and accordingly increases capital or operating costs, forcing either to build additional capacity for the synthesis of alcohol or an alcohol-containing mixture, or purchase methanol (discussed in the example) or other alcohol. In addition, this method has a rather complex system for regulating the supply of different feed streams to different reaction zones.

It should be noted that the use of a multi-reactor scheme, or reactors with several independent reaction volumes, is a natural development of "zeoforming" technologies and its variations (metaforming, aroforming). In particular, it is necessary to note the optimality of the approach using multi-shelf reactors, that is, reactors in which several independent reaction volumes are intentionally smaller relative to one comparable in terms of weight and size characteristics of the reactor, which allow more controlled processing of raw materials and promptly adjust the reaction parameters in each of the reaction zones. This can be confirmed by methods known from the prior art. For example, a method for producing gasolines or concentrates of aromatic compounds [RU 2747870, publication date 05/17/2021] in which three streams are used as raw materials, the first of which includes a hydrocarbon fraction, the second stream includes oxygenate, the third stream includes an olefin-containing fraction, three reaction zones are used , filled with a zeolite catalyst, moreover: the olefin-containing fraction includes from 10 to 50 wt.% C2-C4 olefins and from 0.5 to 8 wt.% hydrogen, the first stream is fed into at least one reaction zone, the second stream is fed into the first reaction zone, or in the third reaction zone, and when the second stream is fed into the first zone, the distribution of the third stream between the two reaction zones is 35-65 wt.% / 65-35 wt.%, and when the second stream is fed into the third reaction zone, the distribution of the third the flow between the two reaction zones is 25-45 wt.% / 75-55 wt.%.

Or the method [WO 2017155424, publication date 09/14/2017], in which the stream of raw materials, similar to the previous method given in the prior art, is purified and then fed into a multi-shelf reactor, where the reaction is carried out in the presence of a zeolite-containing catalyst, the target product of which is high-octane gasoline . At the outlet of the reactor, the conversion product is separated with simultaneous removal of the reaction water and exhaust gases. A reactor is used as a reactor, containing at least two reaction zones, between which there are additional means for mixing the reaction product from the previous reaction zone and the supplied alcohol and olefin-containing raw materials.

However, these solutions, as well as for the prototype, are characterized by a more complex system than those previously considered in the prior art analogues (US 7449420, RU 2103322) for controlling the supply of components, as well as the use of alcohols as raw materials, which, firstly, it causes a poorly controlled process of the passage of uneven volumes of water through the reaction zones during the reaction time, since water is a by-product obtained during the dehydration of the alcohol entering into the reaction, and, secondly, it involves the cost of buying or producing alcohol for the implementation process.

The claimed invention will make it possible to optimize the processes for producing gasolines or concentrated aromatic compounds from available and, as a rule, low-margin raw materials.

The technical result is the creation of a method for the production of gasoline or concentrates of aromatic compounds by co-processing of hydrocarbon fractions and olefin-containing fractions with distributed supply to several series-connected reaction volumes with controlled water supply.

The technical result is achieved by creating a method for producing gasoline fractions and aromatic hydrocarbons, in which the hydrocarbon fraction, the olefin-containing fraction containing one or more olefins selected from the group including ethylene, propylene, normal butylenes, isobutylene, and water are distributed distributed into the reactor filled with a zeolite catalyst and including at least two consecutive independent reaction volumes, or at least two series-connected reactors in such a way that the hydrocarbon fraction is fed into at least the first reaction volume, the olefin-containing fraction and water are also fed into the first reaction volume, into the second and subsequent reaction volumes a mixture of the olifin-containing fraction and water is supplied, or only water, the volumetric supply of water is carried out in the first reaction volume - from 20 to 25% of the total volume of supplied water, in the second and subsequent - the rest, so that water is supplied to each reaction volume, and the volumetric rate of water supply was adjustable, and the proportions of the supplied components are 85-92.7 wt.% hydrocarbons; 3.7-7 wt.% olefin-containing fraction; 2-10 wt% water.

In one of the embodiments of the method, the reaction takes place in two or three reaction volumes.

In one of the embodiments of the method, the hydrocarbon fraction is fed into the first reaction volume, the olefin-containing fraction is fed into the first and second reaction volumes, and water is fed into the first, second and third reaction volumes.

In one of the embodiments of the method, the hydrocarbon fraction is fed into the first reaction volume, the olefin-containing fraction is fed into the first, second and third reaction volumes, water into all reaction volumes.

In one of the embodiments of the method, the hydrocarbon fraction is supplied to the first and second reaction volumes, the olefin-containing fraction is supplied to the first and second reaction volumes, and water is supplied to all reaction volumes.

In one of the embodiments of the method, the hydrocarbon fraction is fed into the first reaction volume and subsequent reaction volumes in such a way that at least 80% of the total volume of the hydrocarbon fraction is supplied to the first volume.

In one of the embodiments of the method, water is distributed in such a way that the same amount or more water is supplied to each subsequent reaction volume than to the previous one.

In one of the embodiments of the method, the hydrocarbon fraction may be, in particular, the propane-butane fraction or the NK-85 °C fraction or the 85-210 °C fraction.

In one of the embodiments of the method for monitoring temperature differences in each reaction volume is located from three temperature sensors.

In one of the embodiments of the method, the reaction is carried out under the following parameters: temperature 320-390 °C, pressure 15-22 atm.

In one embodiment of the process, the olefin-containing fraction is selected from the group consisting of dry catalytic cracking gas, wet catalytic cracking gas, other catalytic cracking gases and their fractionation products, coker off-gas, Fischer-Tropsch synthesis gases, and mixtures thereof.

In one of the embodiments of the method, the olefin-containing fraction is selected from the group including propane-propylene fractions, butane-butylene fractions, thermal cracking gas, visbreaking gas, dry catalytic cracking gas, hydrocracking off-gases, pyrolysis gas, gaseous catalytic reforming wastes, as well as their mixtures.

In one of the embodiments of the method, the product stream after sequential passage of all reaction volumes is divided into a hydrocarbon fraction of the product and an aqueous fraction of the product, and in which the main component of the target liquid hydrocarbon product is C5+ hydrocarbons.

The essence of the claimed invention is as follows. Reactions in a reactor with at least two independent reaction volumes or in several independent series reactors. Raw materials, namely, the hydrocarbon fraction, the olefin-containing fraction and water are supplied, respectively, in the proportion: 85-92 / 3.7-7 / 2-10%. This ensures a distributed supply of raw material flows. The hydrocarbon fraction is fed to at least the first reaction volume. The olefin-containing fraction and water are fed into the first reaction volume. The second and subsequent reaction volumes are fed with a mixture of the olefin-containing stream and water, or only water. The water supply is carried out with the regulation of the volumetric velocity. All components are supplied in the gas phase. Volumetric water supply is carried out in the ratio: in the first reaction volume - 20-40% of the total volume of water, in the second - the rest. When implementing a scheme with three or more reaction volumes, 20% of the total volume of water is supplied to the first one, and 20% of the total volume of water is supplied to the second and subsequent ones - it is distributed between the reaction volumes in such a way that the amount of water that is greater than or equal to the amount of water supplied to the second reaction volume is supplied to the second reaction volume. the first reaction volume, the third - more than the second and so on. In this case, depending on the temperature parameters in different reaction volumes, the water supply rate can be controlled.

The use of water in catalytic refining processes is generally a common practice. However, in the variants of the development of "zeoforming", "aroforming", "metaforming" technologies, it has not yet been practiced to carry out reactions to obtain the target product in a multi-shelf reactor with controlled addition of water to each reaction volume, depending on the reaction parameters in each independent reaction volume, with joint processing of hydrocarbons and olefin-containing fraction on a zeolite catalyst. In the solution according to the invention, the method not only eliminates the additional feed stream characteristic of the prototype, but also continuously monitors and regulates the temperature in the catalyst bed, which reduces catalyst coking and allows you to control the course of side reactions.

According to the experimental data presented in the description of the prototype, during the reaction, along with the gasoline fraction (35-215°C), the formation of a diesel fraction (more than 215°C) also occurs. The proposed solution with the supply of water to the reaction volumes can reduce the formation of the 215°C + fraction on a par with the prototype, however, it also allows you to abandon the raw alcohol flow, as well as provide temperature control in the catalyst bed. In this way, it is possible to achieve a final boiling point of the resulting hydrocarbon product of less than 215°C, as well as a resin content in the product below 5 mg/cm ³ , to ensure uniformity and controllability of the process in terms of temperature, to simplify raw material logistics and, at the same time, to reduce the cost of raw materials used.

The absence of a diesel fraction in the products significantly simplifies the process equipment, since the stage of additional separation of gasoline from the diesel fraction is not required, and the avoidance of overheating of the catalyst reduces the likelihood of its coking and significantly improves its quality and resource characteristics.

The method is carried out as follows:

A zeolite catalyst based on ZSM-5 zeolite is loaded into each reaction volume. The reaction is carried out under the following parameters: temperature 320-420 °C, pressure 1.5-2.4 MPa, preferably: temperature 320-390 °C, pressure 1.5-2.2 MPa. The proportions of the supplied components are 85-92.7% wt. (hydrocarbons) - 3.7-7% wt. (olefin-containing fraction) - 2-10% wt. (water). The reactor used is a typical fixed bed catalytic reactor. Further, water and, depending on the embodiment, the olefin-containing fraction are supplied to the second and, if any, subsequent reaction volumes through the connected process pipelines. The volumetric rate of water supply is an adjustable parameter. To control temperature differences in each reaction volume, there are three temperature sensors, for example, thermocouples, located in the upper part, in the middle and in the lower part of the reaction volume in the catalyst bed. In this case, the larger the reaction volume, the greater the number of temperature control points must be provided to control the uniformity of the temperature field. For example, it is possible to arrange temperature sensors from the center to the walls and more temperature control points in the distribution over the catalyst bed. The need to control the temperature and uniformity of the temperature field is due to the thermal effects of the ongoing reactions. For co-feeding incoming streams, there are mixing zones in front of the first, second and subsequent reaction volumes. Mixing zones can be process volumetric vessels or mixing valves, or other mixing solutions can be used.

The hydrocarbon fraction (hereinafter referred to as HCF; composition options are shown in Table 1), which is a product of an existing oil refinery or purchased raw material, is sent along the process line to the mixing zone before the first reaction volume. As HCF, including, but not excluding, both raw materials rich in olefins (dry catalytic cracking gas, butane-butylene fraction, visbreaking gas) and raw materials with a minimum content of olefins (propane-butane fraction, NK- 85 °С, fraction 85-180 / 85-210 °С). The use of the latter is preferable on the basis of economic prerequisites and due, as a rule, to many times the volumes in oil refining compared to olefin-rich fractions in oil refineries. In this case, for the latter, a separate supply of the olefin-containing fraction was carried out. The olefin-containing fraction includes one or more olefins selected from the group consisting of ethylene, propylene, normal butylenes, isobutylene (composition options according to the tests carried out are shown in table 2). The olefin-containing fraction, which is also a product of an existing oil refining or petrochemical production or purchased raw material, is sent through the production line to the mixing zone.

It is possible to carry out the invention in which the olefin-containing fraction is selected from the group including dry catalytic cracking gas, wet catalytic cracking gas, other catalytic cracking gases and their fractionation products, off-gas from a coker, visbreaking unit, etc., as well as mixtures thereof.

It is possible to carry out the invention, in which the olefin-containing fraction is selected from the group including propane-propylene fractions, butane-butylene fractions, thermal cracking gas, visbreaking gas, dry catalytic cracking gas, hydrocracking off-gases, pyrolysis gas, gaseous catalytic reforming wastes, as well as their mixtures.

A stream of water is also supplied to the reactor.

The supply of water and olefin-containing fraction or only water is also carried out in subsequent reaction volumes. The number of reaction volumes is determined by the performance of the installation, based on the fact that a larger volume is more prone to temperature unevenness across the catalyst bed.

In particular, a zeolite based on ZSM-5 with the following composition was used as a catalyst: 70% ZSM-5 zeolite, 20% Al ₂ O ₃ , 10% SiO ₂ . Granule diameter up to 3.8 mm; mass fraction of particles less than 1 mm, %, not more than 0.5; specific surface 280 m ² /g; pore volume not less than 0.22 cm ³ /g; average pore diameter, Å 53. However, the practice of using zeolite catalysts of a different composition with minor deviations from the described embodiments without compromising the quality of the resulting product is known.

The distribution of water and olefin-containing fraction when fed into various reaction volumes is described in more detail in the examples and is given in tables 3.1 and 3.2.

The product stream after successive passage of all reaction volumes is divided into a hydrocarbon fraction of the product and an aqueous fraction of the product. The aqueous fraction of the product is withdrawn.

The hydrocarbon fraction of the product is further separated into a liquid hydrocarbon product and a gaseous product, in particular by fractionation and stabilization methods. For example, settling and degassing of the aqueous phase, debutanization of the hydrocarbon phase, etc. can be performed. The gaseous product may be further separated into a fraction of the gaseous product enriched in C3-C4 hydrocarbons and a fraction of the gaseous product enriched in C1-C2 hydrocarbons.

The main component of the liquid hydrocarbon product is C5+ hydrocarbons (hydrocarbons with five or more carbon atoms). Depending on the goals of a particular production, a liquid hydrocarbon product may contain not only C5+ hydrocarbons, but also various amounts of dissolved C3-C4 gases. In particular, in the production of motor gasoline, the presence of up to 3-5 wt. % of dissolved gases in summer gasolines and up to 5-7 wt. % of dissolved gases in winter gasolines. The gaseous product may include C1-C4 hydrocarbons, nitrogen, hydrogen and other inorganic gases, as well as heavier hydrocarbons.

Further, the implementation of the invention and its industrial applicability are illustrated by a number of examples. The results and reaction conditions for the examples are given in tables 3.1 and 3.2. The group composition of the liquid hydrocarbon product (wt.%) is given in table 4.

Examples 1-3 are presented to illustrate the processing of olefin-rich feedstock, which, on the one hand, has a high RON in the target product, but on the other hand, the parameters are worse compared to processing with a distributed supply of three streams in terms of yield. It is important to note that the feedstock options given in examples 1-3, firstly, are more marginal refined products than the feedstock presented as the main supply volume in examples 4-15, and secondly, the possible volumes of such feedstock in the oil refining industry, as a rule, at times, and sometimes tens of times lower than the available volumes of raw materials in examples 4-15.

Example 1

The supply of hydrocarbon fraction (UHF) A, and water in the proportion of 93.63/7.37, respectively, was carried out without distributing the incoming streams over several reaction volumes. (hereinafter, the designation of reaction volumes is R)

The volumetric feed rate for the reaction volumes R1/R2/R3 respectively 1718/859/859 h ^-1 . Temperature: 320 °C.

According to the test results, the yield of С5+ per ton of raw materials was 47.46%, RON 107.5. In this example, an olefin-rich feedstock is used as the HCF.

Example 2

The supply of UVF A, and water in the proportion of 92.68 / 7.32, respectively, was carried out distributed over 3 reaction volumes as follows:

UVF: 100% R1. Water: 25% R1; 50% R2; 25% R3.

The volumetric feed rate in the reaction zones R1/R2/R3 respectively 1245/1537/1724 h ^-1 . Temperature: 320 °C.

According to the test results, the yield of С5+ per ton of raw materials was 52.47%, RON 100.6. In this example, an olefin-rich feedstock is used as the HCF.

Example 3

The supply of UVF-B and water in the proportion of 86.45 / 13.55, respectively, was carried out distributed over 2 reaction volumes as follows:

UVF: 100% R1. Water: 20% R1; 80% R2.

The space velocity of the feed in the reaction zones R1/R2/R3 respectively 374/461 h ^-1 . Temperature: 320 °C. In this example, unlike all the others, the pressure was 18 atm.

According to the test results, the yield of С5+ per ton of raw materials was 29.46%, RON 89.8. In this example, an olefin-rich feedstock is used as the HCF.

Example 4

The supply of UVF - G, OF - A and water in the proportion of 86.02 / 6.99 / 6.99, respectively, was carried out distributed over 3 reaction volumes as follows:

UVF: 100% R1.

OF: 20% R1; 20% R2; 60% R3.

Water: 20% R1; 30% R2; 50% R3.

The volumetric feed rate in the reaction zones R1/R2/R3 respectively 149/149/446 h ^-1 . Temperature: 360 °C.

According to the test results, the yield of С5+ per ton of raw materials was 61%, RON 87.9.

Example 5

The supply of UVF - G, OF - A and water in the proportion of 89.36 / 3.65 / 6.99, respectively, was carried out distributed over 3 reaction volumes as follows:

UVF: 100% R1.

OF: 20% R1; 40% R2; 40% R3.

Water: 20% R1; 30% R2; 50% R3.

The volumetric feed rate in the reaction zones R1/R2/R3 respectively 140/280/280 h ^-1 . Temperature: 390 °C.

According to the test results, the yield of С5+ per ton of raw materials was 47%, RON 93.5.

Example 6

The supply of UVF - D, OF - A and water in the proportion of 87.24 / 6.38 / 6.38, respectively, was carried out distributed over 3 reaction volumes as follows:

UVF: 100% R1. RP: 20% R1; 20%R1; 60% R3.

Water: 20% R1; 30% R2; 50% R3.

The volumetric feed rate in the reaction zones R1/R2/R3, respectively, 140/240/419 h ^-1 . Temperature: 360 °C.

According to the test results, the yield of С5+ per ton of raw materials was 94%, RON 81.9.

Example 7

The supply of UVF - D, OF - A and water in the proportion of 89.85 / 3.65 / 6.99, respectively, was carried out distributed over 3 reaction volumes as follows:

UVF: 100% R1. RP: 20% R1; 40% R2; 40% R3.

Water: 20% R1; 30% R2; 50% R3.

The volumetric feed rate in the reaction zones R1/R2/R3 respectively 113/226/226 h ^-1 . Temperature: 390 °C.

According to the test results, the yield of С5+ per ton of raw materials was 72%, RON 90.3.

Example 8

The supply of UVF - B, OF - G and water in the proportion of 92.38 / 3.65 / 3.97, respectively, was carried out distributed over 3 reaction volumes as follows:

UVF: 100% R1. OF: 30% R1; 30% R2; 40% R3.

Water: 20% R1; 20% R2; 60% R3.

The volumetric feed rate in the reaction zones R1/R2/R3 respectively 170/170/226 h ^-1 . Temperature: 390 °C.

According to the test results, the yield of С5+ per ton of raw materials was 120%, RON 88.3.

Example 9

The supply of UVF - G, OF - B and water in the proportion of 92.26 / 3.77 / 3.97, respectively, was carried out distributed over 3 reaction volumes as follows:

UVF: 100% R1. OF: 20% R1; 30% R2; 50% R3.

Water: 20% R1; 20% R2; 60% R3.

The volumetric feed rate in the reaction zones R1/R2/R3 respectively 104/156/260 h ^-1 . Temperature: 360 °C.

According to the test results, the yield of С5+ per ton of raw materials was 90.1%, RON 90.

Example 10

The supply of UVF - D, OF - B and water in the proportion of 92.41 / 3.83 / 3.76, respectively, was carried out distributed over 3 reaction volumes as follows:

UVF: 100% R1. OF: 30% R1; 30% R2; 40% R3.

Water: 20% R1; 20% R2; 60% R3.

The volumetric feed rate in the reaction zones R1/R2/R3, respectively, 156/156/208 h ^-1 . Temperature: 360 °C.

According to the test results, the yield of С5+ per ton of raw materials was 78%, RON 90.5.

Example 11.

The supply of UVF - D, OF - B and water in the proportion of 92.27 / 3.97 / 3.76, respectively, was carried out distributed over 3 reaction volumes as follows:

UVF: 100% R1.

OF: 20% R1; 30% R2; 50% R3.

Water: 20% R1; 20% R2; 60% R3.

The volumetric feed rate in the reaction zones R1/R2/R3 respectively 149/223/372 h ^-1 . Temperature: 390 °C.

According to the test results, the yield of С5+ per ton of raw materials was 68%, RON 92.7.

Example 12.

The supply of UVF - D, OF - B and water in the proportion of 92.52 / 5.48 / 2.0, respectively, was carried out distributed over 3 reaction volumes as follows:

UVF: 100% R1.

OF: 30% R1; 30% R2; 40% R3.

Water: 20% R1; 20% R2; 60% R3.

The volumetric feed rate in the reaction zones R1/R2/R3 respectively 152/152/213 h ^-1 . Temperature: 360 °C.

According to the test results, the yield of С5+ per ton of raw materials was 71%, RON 91.8.

Example 13

In this example, overheating was deliberately carried out in the second reaction volume. At the moment, the temperature was raised to 420 °C. The supply of UVF - D, OF - A and water was initially assumed in the proportion of 87.88 / 5.14 / 6.97, respectively. With a uniform reaction, the distribution over the reaction volumes would be:

UVF: 80% R1; 20% R2.

OF: 40% R1; 60% R2.

Water: 45% R1; 55% R2.

To eliminate overheating, the water supply to the second volume was increased. Due to the additional water supplied to the second volume, the water ratio changed as follows:

Water: 30% R1; 70% R2.

The ratio of all supplied components (UVF - D, OF - A and water) was, respectively:

85.03/4.97/10.0

Due to the adjustable water supply, the temperature regime was returned to the required level - 390 °C.

According to the test results, the yield of С5+ per ton of raw materials was 75%, RON 90.4.

Example 14

The supply of UVF - D, OF - A and water in the proportion of 92.27 / 3.68 / 4.05, respectively, was carried out distributed over 2 reaction volumes as follows:

UVF: 100% R1.

RP: 100% R1.

Water: 40% R1; 60% R2.

The volumetric feed rate in the reaction zones R1/R2/R3 respectively 149/221/221 h ^-1 . Temperature: 390 °C.

According to the test results, the yield of С5+ per ton of raw materials was 72%, RON 90.7.

Example 15

The supply of UVF - D, OF - A and water in the proportion of 89.85 / 4.01 / 6.14, respectively, was carried out distributed over 3 reaction volumes as follows:

UVF: 100% R1.

OF: 30% R1; 70% R2.

Water: 20% R1; 30% R2; 50% R3.

The volumetric feed rate in the reaction zones R1/R2/R3, respectively, 159/241/287 h ^-1 . Temperature: XXX °C.

According to the test results, the yield of С5+ per ton of raw materials was 75%, RON 90.7.

Example 16

The supply of UVF - D, OF - E and water in the proportion of 86.46 / 6.72 / 6.72, respectively, was carried out distributed over 3 reaction volumes as follows:

UVF: 100% R1.

OF: 20% R1; 20% R2; 60% R3.

Water: 20% R1; 30% R2; 50% R3.

The volumetric feed rate in the reaction zones R1/R2/R3 respectively 167/245/399 h ^-1 . Temperature: 360 °C.

According to the test results, the yield of С5+ per ton of raw materials was 87%, RON 82.1.

Examples 17, 18, 19 repeat the conditions, respectively, of examples 9, 6, 13 with the only difference that the water supply was distributed in a different ratio. The results obtained (in terms of octane-ton) turned out to be worse than in the initial experiments, which confirms the effect of the distribution of water by volume, in which each subsequent zone is supplied with a volume of water equal to or greater than the previous one, on the reaction efficiency.

Example 17.

Water: 40% R1; 30% R2; 30% R3.

According to the test results, the yield of С5+ per ton of raw materials was 85.8%, RON 90.6.

Example 18.

Water: 40% R1; 30% R2; 30% R3.

According to the test results, the yield of С5+ per ton of raw materials was 88.3%, RON 84.3.

Example 19.

Water: 50% R1; 50% R2.

According to the test results, the yield of С5+ per ton of raw materials was 72%, RON 91.4.

Table 1. Parameters of hydrocarbon feedstock (% wt.)

Designation Description Compound Normal paraffins Isoparaffins Olefins Naphthenes aromatic hydrocarbons Benzene content Hydrogen Nitrogen A Dry catalytic cracking gas - - 29.4 - - - 2.3 68.4 B Butane-butylene fraction 10.4 55.6 34.1 0 0 0 0 0 IN Propane-butane fraction 79 21 0 0 0 0 0 0 G Fraction NK-85 ⁰ C 45.8 40.8 0.4 11.4 1.6 1.5 0 0 D Fraction 85-180 ⁰ C 27.3 33.3 0.9 29.1 7.0 0.7 0 0 E Visbreaking gas - - 20.5 - - - - -

Table 2. Group composition of olefin-containing fractions (% wt.)

Hydrocarbon fraction A B E Methane 28.0 - 24.4 Ethane 22.5 - 20.6 Ethylene 16.7 0.1 2.9 Propane 1.9 3.4 18.7 Propylene 2.6 2.6 9.4 N-butane 0.3 6.9 2.1 Isobutane 0.2 55.6 7.6 Isobutylene 0.1 3.4 - butenes 0.2 28.1 8.2 From ₅₊ 5.9 0.1 4.1 H ₂ 1.6 - 0.3 N ₂ 20.0 - 1.7 Total 100 100 100

Table 3. Test results

Example 1 2 3 4 5 6 7 8 9 10 eleven 12 13 14 15 16 UVF A A B G G D D G G D D D D D D D OF A A A A B B B B IN A A A E Temperature, ⁰ С 360 320 320 360 390 360 390 390 360 360 390 360 390 390 390 360 Pressure, atm. 22 22 18 22 22 22 22 22 22 22 22 22 22 22 22 22 Hydrocarbon fraction, % R1 100 100 100 100 100 100 100 100 100 100 100 100 80 100 100 100 R2 - - - - - - - - - - - - 20 - - - R3 - - - - - - - - - - - - - - - - Olefin-containing fraction, % R1 - - - 20 20 20 20 thirty 20 thirty 20 thirty 40 100 thirty 20 R2 - - - 20 40 20 40 thirty thirty thirty thirty thirty 60 - 70 20 R3 - - - 60 40 60 40 40 50 40 50 40 - - - 60 Water, % R1 100 25 20 20 20 20 20 20 20 20 20 20 thirty 40 20 20 R2 - 50 80 thirty thirty thirty thirty 20 20 20 20 20 70 60 thirty thirty R3 - 25 50 50 50 50 60 60 60 60 60 - - 50 50 Ratio of raw materials components, total UVF 92.63 92.68 86.45 86.02 89.36 87.24 89.85 92.38 92.26 92.41 92.27 92.52 85.03 92.27 89.85 86.46 OF 6.99 3.65 6.38 3.77 3.65 3.77 3.83 3.97 5.48 4.97 3.68 4.01 6.72 Water 7.37 7.32 13.55 6.99 6.99 6.38 6.38 3.97 3.97 3.76 3.76 2.00 10.00 4.05 6.14 6.72 TOTAL: 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Volumetric feed rate, h ^-1 R1 1718 1245 374 149 140 140 113 170 104 156 149 152 157 149 159 167 R2 1718 1537 461 149 280 240 226 170 156 156 223 152 258 221 241 245 R3 1718 1724 681 446 280 419 226 226 260 208 372 213 258 221 287 399 results Output from / to C5 + per ton of raw materials 47.46 52.47 29.46 61 47 94 72 120 90.1 78 68 71 75 72 75 87 EYES 107.5 100.6 89.8 87.9 93.5 81.9 90.3 88.3 90 90.5 92.7 91.8 90.4 90.7 90.7 82.1

Table 3.2 Examples of testing under different conditions (comparative*)

Example 17(9*) 18(6*) 19(13*) UVF G D D OF B A A Temperature, ⁰ C 360 360 390 Pressure, atm. 22 22 22 Hydrocarbon fraction R1 100 100 80 R2 - - 20 R3 - - - Olefin-containing fraction, distributed feed R1 20 20 40 R2 thirty 20 60 R3 50 60 - Water, % R1 40 40 50 R2 thirty thirty 50 R3 thirty thirty - Ratio of raw materials components, total UVF 92.26 87.24 85.03 OF 3.77 6.38 4.97 Water 3.97 6.38 10.00 TOTAL: 100 100 100 Volumetric feed rate, h ^-1 R1 148 119 194 R2 179 168 258 R3 260 419 258 results Output from / to C5 + per ton of raw materials 85.8 88.3 72 EYES 90.6 84.3 91.4

Table 4. Group composition of the liquid hydrocarbon product (wt.%)

Example 1 2 3 4 5 6 7 8 9 10 eleven 12 13 14 15 16 Paraffins 6.39 8.88 18.05 17.83 11.7 24.85 16.43 13.2 10.25 9.88 6.1 7.12 14.35 13.57 10.84 21.13 Isoparaffins 20.26 27.30 40.93 52.54 46.92 49.05 48.59 39.27 39.35 38.48 37.3 19.44 49.73 45.84 39.31 47.36 Naphthenes 2.12 3.99 3.78 5.61 3.09 6.69 4.11 21.39 15.84 17.77 16.65 3.17 5.78 6.13 5.43 7.19 Olefins 0.10 1.57 1.24 0.51 0.66 1.94 0.84 2.95 3.64 4.54 2.09 2.87 1.87 2.01 1.93 2.01 aromatic hydrocarbons 71.13 58.26 36 23.51 37.63 17.46 30.03 23.18 30.92 29.33 37.89 67.4 28.27 32.45 42.49 22.31 Naphthalene 1.33 1.03 0.46 0.35 0.87 0.31 0.24 0.61 0.7 0.59 0.17 1.95 0.58 0.84 1.01 0.43 Total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Benzene content 6.25 3.48 1.83 1.53 2.99 1.22 2.04 0.79 1.49 1 2.23 5.35 1.89 2.01 2.19 1.43

Claims (13)

1. A method for producing gasoline fractions and aromatic hydrocarbons, in which a hydrocarbon fraction, an olefin-containing fraction containing one or more olefins selected from the group including ethylene, propylene, normal butylenes, isobutylene, and water are distributed distributed into a reactor filled with a zeolite catalyst and including at least two consecutive independent reaction volumes, or at least two series-connected reactors in such a way that the hydrocarbon fraction is supplied to at least the first reaction volume, the olefin-containing fraction and water are also supplied to the first reaction volume, the second and subsequent reaction volumes are supplied a mixture of an olifin-containing fraction and water, or only water, the volumetric supply of water is carried out in the first reaction volume - from 20 to 25% of the total volume of supplied water, in the second and subsequent - the rest, so that water is supplied to each reaction volume, and the volumetric rate of water supply was adjustable, and the proportions of the supplied components are 85-92.7 wt.% hydrocarbons; 3.7-7 wt.% olefin-containing fraction; 2-10 wt.% water. 2. The method according to claim 1, in which the reaction takes place in two or three reaction volumes. 3. The method according to claim 1, in which the hydrocarbon fraction is supplied to the first reaction volume, the olefin-containing fraction is supplied to the first and second reaction volumes, water is supplied to the first, second and third reaction volumes. 4. The method according to claim 1, in which the hydrocarbon fraction is fed into the first reaction volume, the olefin-containing fraction is fed into the first, second and third reaction volumes, water - into all reaction volumes. 5. The method according to claim 1, in which the hydrocarbon fraction is supplied to the first and second reaction volumes, the olefin-containing fraction is supplied to the first and second reaction volumes, water is supplied to all reaction volumes. 6. The method according to claim 1, in which the hydrocarbon fraction is supplied to the first reaction volume and subsequent reaction volumes in such a way that at least 80% of the total volume of the hydrocarbon fraction is supplied to the first volume. 7. The method according to claim 1, in which water is supplied distributed in such a way that each subsequent reaction volume is supplied with water as much or more than the previous one. 8. The method according to claim 1, in which the hydrocarbon fraction may be in particular a propane-butane fraction or a NK-85 °C fraction or a 85-210 °C fraction. 9. The method according to claim 1, in which to control temperature differences in each reaction volume is located from three temperature sensors. 10. The method according to claim 1, in which the reaction is carried out under the following parameters: temperature 320-390 ° C, pressure 15-22 atm. 11. The process of claim 1, wherein the olefin-containing fraction is selected from the group consisting of dry catalytic cracking gas, wet catalytic cracking gas, other catalytic cracking gases and their fractionation products, coker off-gas, Fischer-Tropsch synthesis gases, and their mixtures. 12. The process of claim 1, wherein the olefin-containing fraction is selected from the group consisting of propane-propylene fractions, butane-butylene fractions, thermal cracking gas, visbreaking gas, dry catalytic cracking gas, hydrocracking off-gases, pyrolysis gas, catalytic reforming off-gases , as well as their mixtures. 13. The method according to claim 1, in which the product stream after sequential passage of all reaction volumes is separated into a hydrocarbon fraction of the product and an aqueous fraction of the product, and in which the main component of the target liquid hydrocarbon product is C5+ hydrocarbons.