EA021358B1 - Catalyst, method for the production thereof and method for producing a mixture of hydrocarbons having a low content of aromatic compounds - Google Patents

Abstract

The invention relates to the field of producing hydrocarbons from dimethyl ether, in particular, a mixture of hydrocarbons of the benzine series having a low content of aromatic compounds, which mixture is basically an analogue of gaseous condensate. The technical problem is to reduce the content of aromatic compounds and to increase the productivity of the process. The catalyst for the synthesis of a mixture of hydrocarbons having a low content of aromatic hydrocarbons comprises 0.5-2.0% by mass of zinc oxide, or 0.2-1.0% by mass of zirconium oxide, and/or 0.2-1.0% by mass of lanthanum oxide, 0.1-1.0% by mass of palladium, 65.0% by mass of a pentasil-type zeolite containing SiO/AlO=25-100, comprising a maximum of 0.1% by mass of sodium oxide, with the remainder being a binder. To produce a catalyst an ammonium form of zeolite is first of all modified with aqueous solutions of lanthanum nitrate and/or zirconium nitrate, the modified zeolite is dried and calcined, after which an aqueous solution of zinc nitrate is introduced into the zeolite under ion-exchange conditions, a binder is added and extrudates are prepared, the latter again being dried and calcined, and then the catalyst extrudates are impregnated with an aqueous solution of palladium chloride, followed by drying and calcining again. The synthesis of a mixture of hydrocarbons from gases comprising dimethyl ether and a synthesis gas comprising at least 71% by mass of a hydrogen is carried out in the presence of above catalyst in a circulation mode at a circulation rate of 10-35.

Description

The present invention relates to a method for producing hydrocarbons from dimethyl ether (a synthesis gas conversion product, one of the sources of which is associated petroleum gas), in particular a mixture of hydrocarbons of a gasoline series with a low content of aromatic compounds, which is similar in composition to a gas condensate.

State of the art

Currently, associated petroleum gas (APG) in the fields is mostly flared (more than 20%) and only partially used. Effective methods of chemical processing of associated petroleum gas, implemented on an industrial scale directly in the fields, are practically absent.

The use of associated gas as a chemical feedstock is hindered mainly by the fact that a significant part of the associated gas is produced in small deposits that are remote from traditional processing centers. In such fields, they try not to mess with the creation of infrastructure for the collection, compression, transportation and processing of associated gas, since this requires significant energy, capital and operating costs, as well as additional energy costs for the compression of associated gas. In addition, it is well known that OTB synthesis (gas to liquid conversion) is better than purification. In synthesized products, it is much easier to control the level of impurities. This means that, in principle, they are much cleaner than petroleum products produced in the traditional way.

A feasible way to solve the problem of APG utilization is to use modular multi-purpose plants for APG processing using OT technology to produce a variety of organic products: Fischer-Tropsch synthetic oil for pumping into the pipeline, motor fuels (e.g. gasoline, diesel fuel, etc.) and other chemical products (e.g. methanol).

However, the orientation of the APG processing scheme to the production of methanol or high-octane gasoline is possible only if the developed network of target consumers does not resolve the issue of building a pipeline or organizing transport. According to the Fisher-Tropsch APG processing scheme, a wide hydrocarbon fraction is obtained, including both aliphatic compounds and unsaturated and oxygen-containing hydrocarbons, which makes it impossible to use it as gas condensate without additional processing.

For this reason, one of the most attractive solutions to the problem of APG utilization is its processing using OT technology from gas mixtures containing DME into a mixture of gasoline hydrocarbons with a low content (less than 5 wt.%) Of aromatic compounds - an analogue of gas condensate. The return of the condensate thus obtained into the oil pipeline will increase the degree of beneficial use of the oil well.

All known methods for producing gasoline hydrocarbons from gas mixtures containing DME are aimed at producing high-octane gasoline components with a high content of aromatic hydrocarbons.

These methods can be divided into two groups:

two-stage methods for producing hydrocarbons from synthesis gas through DME and / or methanol with the release of an intermediate product, which are described in patents No. KI 2143417, AO 2006/126913 A2, KI 2226524, or without isolation of an intermediate product, as, for example, in US patent No. 4,481,305; 4,520,216;

one-stage processes in which the stage of synthesis of the intermediate product and the stage of synthesis of hydrocarbons are carried out in one reactor.

The raw material for producing hydrocarbons according to the listed patents is synthesis gas, and each patent uses a specific composition of synthesis gas, which does not always correspond to those compositions that can be obtained by known processes for its production. To achieve the desired result, circulation of gas flows is used.

However, a common drawback of the technical solutions described in these patents is the high content of aromatic hydrocarbons - more than 20 wt.%.

Close to the technical result is a one-stage method for producing hydrocarbons described in patent No. KI 2175960. The feedstock for the process is synthesis gas of the composition N ₂ - 68; СО - 28; CO ₂ - 3; CH ₄ - 1 vol.% On a catalyst consisting of a ΖδΜ-5 type zeolite (with 8Su ₂ / A1 ₂ Oz = 70) and a metal oxide component containing ΖηО, Cr ₂ O ₃ and A ₂ O ₅ . The process is carried out under rather severe conditions (temperature 360-420 ° C, pressure 8-10 MPa and high volumetric feed rates 2005000 h ^-1 ). To achieve a technical result, gas circulation is used with a multiplicity of 70-1000 of the volume of circulating gas per volume of the source gas (v / v).

The result is a product with an aromatic content of up to 30 wt.%. A lower aromatic hydrocarbon content of 2.7 wt.% Was obtained by the authors during the semi-industrial process using a shelf adiabatic reactor with cold gas flows between the shelves by the same technical solution. In this case, the yield of liquid hydrocarbons is 1 021358 significantly reduced.

Another disadvantage of this process is the problem of heat removal in the reaction zone, since the production of C ₅ + hydrocarbons goes through the stages of methanol and / or DME production. During the formation of DME, heat is generated from the synthesis gas (70 kcal / mol). The same amount of heat is generated during the formation of gasoline from oxygenates. When combining these two processes in one reactor, the problem of removing the heat of the reaction arises, which can be solved by using high multiplicity of circulation. However, carrying out a process with a high circulation ratio (up to 1000 vol./about.) Complicates the stage of gasoline separation from a very dilute mixture and complicates the implementation of this process on an industrial scale.

A known method of producing a mixture of liquid hydrocarbons enriched in isoparaffins from DME in a two-stage process.

A known method of producing high-octane components of motor gasolines from a highly diluted gas mixture containing DME in an amount of 3.2 wt.%, Described in patent KI No. 2160160 C1, Β0Π 29/40.

According to this invention, a crystalline aluminosilicate of the pentasil type with a ratio δί0 ₂ / Α1 ₂ 0 ₃ = 25-100 containing (wt.%) Is used as a catalyst:

sodium oxide - 0.05-0.1; zinc oxide - 0.5-3.0;

rare earth oxides (REE) - 0.1-5.0; binder component.

The zeolites used in the composition of the indicated catalyst are obtained by direct synthesis or by exchanging the initial IA form of the zeolite for an H + or IN + ₄ form. As a binder component can be used synthetic aluminosilicates, alumina. To modify zeolites, an REE nitrate industrial concentrate containing 200 g of REE oxides was used as a source of REE. The resulting catalyst is preliminarily subjected to activation in an air stream at 540-560 ° C. Then a mixture of the following composition (wt.%) Is passed over the catalyst: Ν ₂ - 66.0, СО - 12.0, СО ₂ - 3.3, Н ₂ -15.5, DME - 3.2 at a temperature of 250- 400 ° C, a pressure of 0.1-10 MPa and a volumetric feed rate of gas raw materials of 250-1100 h ^-1 According to the prototype, the following hydrocarbon products (wt.% In a mixture of hydrocarbons) are obtained as a result of the catalytic conversion of DME (98-100%): С _1- C ₄ - 7.6-16.6, n-paraffins C ₅ + - 2.1-3.2, isoparaffins C ₅ + - 31.1-34.3, other C ₅ + - 20.8- 40.0, aromatic C ₆ + - 15.6-28.8.

The disadvantage of the described method is the relatively low content of isoparaffins: in the liquid products of the process, it does not exceed 34 wt.%.

Closest to the claimed technical solution are:

a catalyst for the synthesis of liquid hydrocarbons from dimethyl ether, described in patent KI No. 2248341 C1, C07C 1/20, Β011 29/44, publ. 03/20/2005, based on a crystalline aluminosilicate of the type of pentasils with 8 с0 ₂ / Α1 ₂ 0 ₃ = 25-100, containing 0.05-0.1 wt.% Sodium oxide, zinc oxide, palladium and a binder, in the following ratio of components wt. %: ΖηΟ - 0.1-3.0; palladium - 0.1-1; crystalline aluminosilicate - 50 -70 and a binder that allows the production of high-octane components of motor fuels from gases containing dimethyl ether;

a catalyst preparation method, carried out by modifying pentasil-type zeolites with 8ί0 ₂ / Α1 ₂ 0 ₃ = 25-100, containing 0.05-0.1 wt.% sodium oxide, 0.1-3 wt.% zinc oxide, and mixing with a binder, and zinc modification is carried out by the method of residual impregnation of a zeolite or a binder or by the method of zeolite ion exchange before mixing it with a binder from an aqueous solution of zinc nitrate in an amount providing a zinc oxide content in the catalyst of 0.1-3 wt.%, and then palladium is introduced residual impregnation method, providing soda neighing of palladium in the catalyst 0.1-1 wt.%;

The method of producing environmentally friendly gasoline or its components with an octane rating of 92-93 according to the research method from raw materials containing up to 15 wt.% DME and water vapor in a molar ratio of 2> H ₂ O / DME> 0 in the presence of the described catalyst, the feed being supplied into the reactor with a space velocity of 1000-4000 h ^-1 . The presence in the feed of various amounts of hydrogen, carbon oxides, nitrogen, methane, methyl alcohol. Their content depends on the composition of the initial synthesis gas and the synthesis mode of DME.

The disadvantage of this method and the catalyst for its implementation is the high content of aromatic hydrocarbons - up to 30 wt.% And low productivity of the process. In this case, it does not exceed 30 g / m ^{3 of} synthesis gas.

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Disclosure of invention

The objective of the proposed technical solution is to develop a method for the synthesis of a mixture of hydrocarbons of a gasoline series with a low content of aromatic compounds from raw materials containing dimethyl ether and synthesis gas (CO, CO ₂ and H ₂ ), similar in composition to gas condensate and suitable, depending on certain tasks, for injection into the oil pipeline to increase the profitability and productivity of the oil well or into the main pipeline, with the aim of transporting it to production facilities, as well as in the development of catalysis ora for such a process and method for its preparation.

The problem is solved by the fact that the proposed catalyst for the synthesis of a mixture of hydrocarbons with a low content of aromatic hydrocarbons based on crystalline aluminosilicate - a zeolite of the pentasil type with δίΟ ₂ / Α1 ₂ Ο ₃ = 25-1 () (). containing not more than 0.1 wt.% sodium oxide, zinc oxide, palladium and a binder, which additionally contains zirconium oxide and / or lanthanum oxide in the following ratios of components, wt.%:

zinc oxide 0.5-2.0 zirconium oxide 0.2-1.0 and / or lanthanum oxide 0.2-1.0 palladium 0.1-1.0 specified zeolite 65.0 binder rest.

The problem is also solved by the fact that the proposed method for producing the described catalyst for the synthesis of mixtures of hydrocarbons with a low content of aromatic hydrocarbons, comprising modifying a zeolite of the pentasil type with 8ίΟ ₂ / Α1 ₂ Ο ₃ = 25-100, containing not more than 0.1 wt.% Sodium oxide , zinc oxide and palladium, mixing with a binder, molding the extrudates, drying and calcining, in which the ammonium form of the zeolite is first modified with aqueous solutions of lanthanum nitrate and / or zirconium nitrate, taken in quantities that provide soda burning in the finished catalyst zirconium oxide 0.2-1.0 wt.% and / or lanthanum oxide 0.2-1.0 wt.%, the modified zeolite is dried and calcined, after which an aqueous solution of nitrate is introduced into the zeolite under ion exchange conditions zinc, taken in an amount that ensures the content of zinc oxide in the finished catalyst, equal to 0.5-2.0 wt.%, add a binder and prepare the extrudates, which are again dried and calcined, then the extrudates of the catalyst are impregnated with an aqueous solution of palladium chloride, taken in an amount providing palladium in ready ohm catalyst, equal to 0.1-1.0 wt.%, and again dried and calcined to form oxides of the corresponding metals.

The problem is also solved by the fact that the proposed method for the synthesis of a mixture of hydrocarbons from gases containing dimethyl ether, synthesis gas (CO, CO ₂ and H ₂ ) in the presence of a catalyst, the process being conducted in a circulating mode with a circulation rate of 10-35, as gas mixtures use a gas mixture with a hydrogen content of not less than 71 vol% in the used synthesis gas, and the catalyst described above as a catalyst.

Moreover, the process of producing a hydrocarbon mixture is carried out in a flowing isothermal high-pressure reactor at a temperature of 320-380 ° C, a pressure of 5-10 MPa, a weighted feed rate of DME of 2.7-10.6 h ^-1 and a linear velocity of the gas mixture of 0.2-0 , 5 m / s (at n.o.).

The technical result from the use of the proposed technical solution is to obtain a mixture of gasoline hydrocarbons with a low content of aromatic compounds equal to not more than 8.0 wt.%, Including durene - not more than 0.7 wt.%, Which is similar in composition to gas condensate ;

an increase in process productivity up to 120 g / m ^{3 of} synthesis gas compared to 30 g / m ^{3 of} synthesis gas according to the prototype.

An additional technical result is an increase in catalyst service (at least 1 month of operation without regeneration).

The invention is illustrated by the following examples, confirming the effectiveness of the proposed method for producing a mixture of hydrocarbons of a gasoline series with a low content of aromatic compounds.

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BEST MODE FOR CARRYING OUT THE INVENTION Obtaining catalyst samples

Example 1

The zeolite used to prepare the catalyst is a domestic analogue of pentasil CVM with a molar ratio of 8ΐΟ ₂ / Α1 ₂ Ο ₃ = 35 (TU 38.401528-85). In order to change the acid properties of the zeolite, an ion exchange of its ammonium form is carried out with an aqueous solution of lanthanum nitrate, taken in an amount providing a lanthanum oxide content in the finished catalyst equal to 0.4 wt.%. After drying at 100 ° C for 12 hours, the powder of the zeolite thus modified is calcined at 500 ° C for 4 hours. Next, an aqueous solution of zinc nitrate, taken in an amount ensuring the content of zinc oxide in the finished catalyst equal to 1.0 wt.%, and then add the calculated amount of a binder (aluminum hydroxide) for the preparation of extrudates. After drying in air, the obtained extrudates are dried at 100-110 ° C for at least 12 hours, then calcined at 500 ° C for 6 hours. The calcined extrudates of the catalyst are impregnated with an aqueous solution of RdC1 ₂ , taken in an amount that ensures the content of Ρά in the finished catalyst equal to 0.5 wt.%, dried at 100-110 ° C for 12 hours and calcined in air at 500 ° C for 4 hours until the formation of oxides of the corresponding metals.

The composition of the obtained catalyst is given below, wt.%:

ΖηΟ - 1.0 ba ₂ 0 - 0.4 palladium - 0.5 zeolite - 65.0 binder - 33.1

Example 2

The catalyst is prepared analogously to example 1, with the difference that they take a solution of lanthanum nitrate in an amount providing a content of lanthanum oxide in the finished catalyst of 0.6 wt.%.

Get the catalyst composition, wt.%:

ΖηΟ-1.0 ba ₂ 0 - 0.6 palladium - 0.5 zeolite - 65.0 binder - 32.9

Example 3

The catalyst is prepared analogously to example 1, with the difference that instead of an aqueous solution of lanthanum nitrate, an aqueous solution of nitric acid zirconyl taken in an amount providing a zirconium oxide content in the finished catalyst equal to 0.4 wt.% Is used. The composition of the obtained catalyst is given below, wt.%:

ΖηΟ-1.0 ΖγΟ ₂ - 0.4 palladium - 0.5 zeolite - 65.0 binder - 33.1

Example 4

The catalyst is prepared analogously to example 3, with the difference that they take an aqueous solution of zirconyl nitrate in an amount providing a content of zirconium oxide in the finished catalyst equal to 0.8 wt.%. The composition of the obtained catalyst is given below, wt.%:

ΖηΟ-Ι, Ο ΖγΟ ₂ - 0.8 palladium - 0.5 zeolite-65.0 binder - 32.7

Example 5

The catalyst is prepared analogously to Example 1, with the difference that after the zeolite is treated with an aqueous solution of lanthanum nitrate, an additional treatment is carried out with an aqueous solution of nitric acid cir-4 021358 conil, taken in an amount that provides the content of ΖγΘ ₂ and La ₂ O ₃ in the finished catalyst equal to 0 , 4 and 0.6 wt.%, Respectively.

The composition of the obtained catalyst is given below, wt.%:

ΖηΟ- 1.0 ΖγΟ ₂ - 0.4 Lа ₂ 0з- 0.6 palladium - 0.5 zeolite - 65.0 binder - 32.5

Example 6

The catalyst is prepared analogously to example 1, with the difference that the modification of the zeolite is carried out by sequential processing of its ammonium form, first with an aqueous solution of nitric acid lanthanum, and then with an aqueous solution of nitric acid zirconyl taken in an amount providing the content of ΖγΟ ₂ and bа ₂ О ₃ in the finished catalyst, equal to 0.8 and 0.6 wt.%, respectively.

The composition of the obtained catalyst is given below, wt.%:

ΖηΟ-1.0 ΖγΟ ₂ - 0.8 La ₂ O ₃ - 0.6 palladium - 0.5 zeolite - 65.0 binder - 32.1

A method of obtaining a mixture of hydrocarbons with a low content of aromatic compounds

Examples 7-12.

The catalysts obtained in examples 1-6 are used to obtain a mixture of hydrocarbons of a gasoline series with a low content of aromatic compounds from raw materials containing dimethyl ether, carbon oxides and hydrogen in a circulation mode with a circulation ratio of 10 to 35 vol./about. in a flow isothermal high-pressure reactor at a temperature of 320-380 ° C, a pressure of 5-10 MPa, a weighted feed rate of DME of 2.7-10.6 h ^-1 .

Before the experiment, catalyst samples are activated in a hydrogen stream (P = 0.1 MPa, ν = 5 l / h) at a temperature rise of 50 ° / h.

Upon reaching the operating temperature, the catalyst sample is kept in this mode for 3 hours. Then, the hydrogen supply is stopped and the feed is started.

The raw material used is a model gas mixture composed of vapors of dimethyl ether and synthesis gas composition (in vol.%): Ν ₂ - 4.0; СО - 21.0; СО ₂ - 3.0; H ₂ - 72.0.

The conditions for the described method and the characteristics of the resulting mixture of hydrocarbons are given in table. one.

Example 13 (comparative prototype).

The catalyst obtained by the method described in the prototype is used to obtain a mixture of hydrocarbons of a gasoline series with a low content of aromatic compounds from raw materials containing dimethyl ether in a flow isothermal high pressure reactor under the conditions given in examples 7-12.

The characteristics of the resulting mixture of hydrocarbons in the conditions of the proposed technical solution, but in the presence of a catalyst obtained by the prototype, are given in table. one.

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Table 1

Conditions of experience and basic indicators Example No. 7 8 nine 10 eleven 12 thirteen Catalyst in one 2 3- 4 5 6 comparator hydrocarbon synthesis reactor according to example No. prototype Pressure, MPa 10 7 10 5 10 10 10 Temperature T, ° С 320 360 340 380 340 340 340 DME weight rate, h ‘ 2.7 8.0 5.3 2.7 10.6 5.3 5.3 The multiplicity of circulation, vol./about. 35 fifteen twenty 10 fifteen twenty twenty DME conversion,% 98.4 97.9 98.9 99.0 98.7 99.8 96.2 The composition of the gasoline fraction, wt.% N-paraffins 9.1 10.6 8.6 9.2 10.5 9.8 9.2 Iso paraffins 73.1 75.7 74,2 77.1 71.9 76.8 61.5 cycloparaffins 9.1 5.8 9.2 8.3 9.5 8.9 7.5 Aromatic UV Including: 7.9 7.0 7.5 4.8 7.6 4.4 20,0 durol 0.7 0.5 0.5 0.2 0.6 0.3 1.8 The output of Sz + on y / in, wt. % 81.3 80.5 83.0 79.1 82.7 84.6 75.8 Performance, 118 117 120 118 120 119 Up to 30 g / m ³ SI gas

Example 14

The catalyst obtained in example 6 is used to obtain a mixture of hydrocarbons of a gasoline series with a low content of aromatic compounds from a mixture of CO, CO ₂ and H ₂ through dimethyl ether without intermediate isolation in a double-circuit reaction unit consisting of a DME synthesis reactor and a hydrocarbon synthesis reactor, united by a single circulation circuit. When using the proposed catalyst in the process of producing hydrocarbons from synthesis gas, a mixture of hydrocarbons with a low content of aromatic compounds is obtained in high yield.

The proposed catalyst obtained in example 6, provides a long (more than 1 month) mileage without regeneration.

The results are presented in table. 2.

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table 2

Experience conditions and key indicators Test duration, hours one hundred 300 600 Pressure in the circuit, MPa 10 T of the second stage, ° C 340 The composition of the synthesis gas, vol.% H2 72 With 21 CO2 3 N2 4 About. fresh gas feed rate (total catalysts 1 704 and 2 stages), h ' ¹ Multiplicity of circulation (vol./vol.) 10 Discharge volume, l / h 5 DME conversion,% 99.9 100.0 99.8 The composition of the gasoline fraction, wt. %: Iso paraffins 79.9 78.6 80.3 N-paraffins 6.9 6.8 6.6 cycloparaffins 8.9 9.1 8.7 Aromatic UV Including: 3,5 5.1 3.8 durol 0.4 0.4 0.6 The output at / in, wt.% 80.3 81.0 79.6 Performance, 119 120 118 g / m ³ SI gas

Industrial applicability

The invention can be applied in the processes of producing hydrocarbons from dimethyl ether (a synthesis gas conversion product, one of the sources of which is associated petroleum gas), in particular a mixture of gasoline hydrocarbons with a low content of aromatic compounds equal to not more than 8.0 wt.%, In including durene - not more than 0.7 wt.% (compared to 30 wt.% according to the prototype), which is an analogue of gas condensate in its composition and suitable, depending on various tasks, for pumping into an oil pipeline to increase profitability and P the productivity of an oil well or in a main pipeline for the purpose of transporting it to production facilities.

The proposed solution allows to increase the productivity of the process up to 120 g / m ³ synthesis gas compared with 30 g / m ³ synthesis gas according to the prototype.

The proposed technology is promising for application at production sites and is an original and economical solution to the acute problem of today - the problem of APG utilization and is intended, first of all, to eliminate flares and reduce the dependence of oil fields on the import of methanol and other petroleum products through the disposal and processing of valuable hydrocarbon feed contained in APG.

Claims (3)

CLAIM 1. The catalyst for the synthesis of a mixture of hydrocarbons with a low content of aromatic hydrocarbons based on crystalline aluminosilicate - a zeolite of the pentasil type with 8ί0 ₂ / Α1 ₂ 0 ₃ = 25-100, containing not more than 0.1 wt.% Sodium oxide, zinc oxide, palladium and a binder , characterized in that it further comprises zirconium oxide and / or lanthanum oxide in the following ratio of components, wt.%: zinc oxide -0.5-2.0 zirconium oxide -0.2-1.0 and / or lanthanum oxide -0.2-1.0 palladium -0.1-1.0 specified zeolite -65.0 binder - the rest. 2. A method for producing a catalyst for the synthesis of a mixture of hydrocarbons with a low content of aromatic hydrocarbons according to claim 1, comprising modifying a zeolite of the pentasil type with 8ί0 ₂ / Α1 ₂ 0 ₃ = 25-100, containing not more than 0.1 wt.% Sodium oxide, zinc oxide and palladium, mixing with a binder, molding the extrudates, drying and calcining, in which the ammonium form of the zeolite is first modified with aqueous solutions of lanthanum nitrate and / or zirconium nitrate, taken in amounts that provide 0.2-1.0 zirconium oxide in the finished catalyst wt.% and / and and lanthanum oxide 0.2-1.0 wt.%, the modified zeolite is dried and calcined, after which an aqueous solution of zinc nitrate, taken in an amount providing the content of zinc oxide in the finished catalyst equal to 0, is introduced into the zeolite under ion exchange conditions , 5-2.0 wt.%, Add a binder and prepare the extrudates, which are again dried and calcined, then the extrudates of the catalyst are impregnated with an aqueous solution of palladium chloride, taken in an amount providing a palladium content in the finished catalyst equal to 0.1-1.0 wt.%, and again dried and calcined removed to form the corresponding metal oxides. 3. A method of synthesizing a mixture of hydrocarbons from gases containing dimethyl ether, synthesis gas (C0, C0 ₂ and H ₂ ), in the presence of a catalyst, the process being carried out in a circulating mode with a circulation rate of 10-35, using a mixture of gases as a mixture of gases with a hydrogen content in the used synthesis gas of at least 71 vol.%, and as a catalyst, the catalyst according to claim 1.