Method of aromatising non-aromatic hydrocarbons

FIELD: chemistry.

SUBSTANCE: invention relates to a method of aromatising non-aromatic hydrocarbons contained in a hydrogenated fraction of a C6-C8 pyrolysis condensate. The method involves reaction of starting material with a metal-containing zeolite aromatisation catalyst at high temperature, and is characterised by that the starting material is a hydrogenated fraction of a C6-C8 pyrolysis condensate containing not less than 70 wt % aromatic hydrocarbons and 8-30 wt % non-aromatic hydrocarbons. The aromatisation catalyst used is a zeolite having entrance window diameter 5.1-7.3Ǻ, having molar ratio of silicon to aluminium equal to 25-140, modified with metals selected from: zinc, gallium, silver, rhodium, platinum, rare-earth elements, as well as combinations thereof.

EFFECT: invention increases output of the end product - benzene and reduces output of light hydrocarbon fractions when processing pyrolysis condensate.

7 cl, 42 ex, 4 tbl

 

The invention relates to the field of organic chemistry and can be used for processing of pyrolysis condensate (pyrolysis condensate fraction) is a by - product of ethylene production in order to convert paraffins and naphthenes contained in the pyrolysis condensate fraction, aromatic hydrocarbons.

(Used in the present invention, the term" pyrolysis condensate fraction refers to the by-product of ethylene production). Used in the present invention, the term "pyrolysis condensate fraction represents the fraction of liquid pyrolysis products with a boiling point less than 200°C. One of the sources of pyrolysis condensate fraction are industrial furnaces for ethylene production. Depending on the type of feedstock the quantity of pyrolysis condensate fraction is from 2 to 20% of the raw material supplied to the pyrolysis. In the process condensate are usually isolated fraction With6-C8having the boiling temperature of 70-150°C. Mentioned fraction is 65-75% of the total weight of the pyrolysis condensate fraction and is characterized in that it contains mainly aromatic hydrocarbons: benzene, toluene, xylenes (BTX), as well as olefins, diene, naphthenes.

In world practice, the fraction With6-C8the pyrolysis condensate fraction is usually subjected to Hydrotreating is used for hydrogenation of olefins and dienes and desulfurization. After Hydrotreating is possible to carry out extraction-destillat the traditional division of fractions in commodity products, or you can hydrodealkylation, wherein the alkylaromatic hydrocarbons are converted into the target product - benzene and non-aromatic hydrocarbons craterous with obtaining light hydrocarbons.

A known method of producing benzene from hydrocarbon benzylideneamino mixtures of different origin, which combines rectification with two-stage catalytic hydrogenation of obtaining hydrocarbon fractions With6-C8and hydrodealkylation of the obtained fractions. In this part of the hydrocarbon fractions With6-C8after hydrogenation is subjected to an additional distillation with the selection from the top of the column of product containing from 30 to 95 wt.% benzene content in the original hydrocarbon fractions With6-C8and VAT residue, containing the remainder of the benzene and aromatic and nonaromatic hydrocarbons, C7-C8which is sent to hydrodealkylation. The product, containing from 30 to 95 wt.% benzene content in hydrocarbon fractions With6-C8, is subjected to extractive distillation with a selective solvent (EN 2291892, 20.01.2007).

A known method of producing benzene from mixtures containing benzene and/or alkyl benzenes with a high content of sulfur-containing substances. The method consists of hydrodealkylation shows the connection with a partial refund nebelkorona component on the stage of hydrodealkylation as recycling, and submission to the specified recycling reference to ha fractions with a high content of sulfur-containing substances, mostly not more than 1.5 wt.% sulphur and aromatic content6-15not less than 60%. According to this method the flow chart of processing in the benzene aromatic fractions of liquid products of pyrolysis and/or carbonization of coal, with boiling points between 60 to 340°C involves a two-stage hydrogenation on palladium sulfide and aluminoborosilicate catalysts and subsequent hydrocracking of paraffin compounds and thermal hydrodealkylation aromatic compounds (toluene, o-, m-, p-xylenes, ethylbenzene) to benzene. The product is then sequentially fed to the stabilization of the column, the column pre-distillation, catalytic reactor purification and benzene column (EN 2193548, 27.11.2002).

A known method of producing benzene, according to which alkylaromatic compounds (BTK fraction of the pyrolysis condensate fraction, or aromatic concentrate process of aromatization liquefied gases or pure toluene), hydrogen, phenolic fraction (or other oxygen-containing aromatic fraction and recycling the unreacted compounds is heated to the temperature of the beginning of the process hydrodealkylation (580-620°C) and sent to the reactor, where the temperature is 20-740°C. Coming out of the reactor the flow sephirot, separating hydrogen gas from liquid hydrocarbons and water. Liquid hydrocarbons is fed to the rectification. From the cube columns display resinous compounds, and the distillate is fed into the reactor units. The purified stream is fed to the column selection trademarks of benzene. Benzene derive from one of the upper plates of the column, and the upper and waste streams returned as recycle to the process (EN 2290393, 27.12.2006).

The above methods are quite complicated. In addition, in the above-described methods for producing benzene contained in gidrirovannoe fraction of the pyrolysis condensate fraction paraffins and naphthenes in the process of hydrodealkylation are cracking with the formation of light hydrocarbons, which leads to loss of valuable hydrocarbons.

A method of obtaining aromatic hydrocarbons and lower olefins, in which the catalytic dehydrocyclization hydrocarbons (paraffins2-C6in the presence of zinc-containing zeolite catalyst, share products dehydrocyclization by gas-liquid separation on the product And aromatic hydrocarbons6+and the product is a mixture of nah With1-C6with hydrogen, conduct hydrodealkylation product And obtaining a commercial benzene and the pyrolysis product is obtaining lower olefins. Products from hydrodealkylation allocate commodity benzene, methane and ethane fraction. Of the gaseous pyrolysis products emit commodity ethylene and propylene, liquid products of pyrolysis - pyrolysis condensate fraction containing aromatic hydrocarbons, is subjected to hydrogenation and hydrodesulphurization unit and subsequent hydrodealkylation with obtaining commercial benzene, methane and ethane fractions, last recyclist on pyrolysis (EN 2370482, 20.10.2009).

Light hydrocarbons obtained in the above and similar methods, is used as the fuel gas, the yield of valuable aromatic hydrocarbons (benzene) this technology is not sufficiently high.

Thus, it seems reasonable to increase the yield of aromatic hydrocarbons from recycled materials, subjecting him flavoring.

There are plenty of aromatization catalysts, for example metal-containing zeolites are described, for example, in SU 1608920, 20.10.1995, EN 2098455, 10.12.1997, EN 2092240, 10.10.1997, EN 2367643, 10.04.2008.

The closest in technical essence and the achieved result is a way of flavoring nah, according to which the stream of hydrocarbons containing gidrirovannoe fraction With6-C8the pyrolysis condensate fraction, serves to interact with the metal-containing zeolite was pushing the congestion flavoring, representing pre dealuminated zeolite ZSM-5 with a molar ratio of silicon to aluminum 2-200 modified with a metal selected from the range: Nickel, palladium, molybdenum, gallium, platinum, when the feedstock contains about 30% paraffins, about 8% naphthenes, about 23% of olefins and 32-33% of aromatic compounds (benzene, toluene, xylenes). The interaction is carried out at 450-650°C., at a molar ratio of hydrogen to hydrocarbon raw materials equal to 2:1 (US 6593503, 15.07.2003, example 4, table 4).

The disadvantage of this method is that it is not effective for flavoring raw material which contains a significant amount of aromatic compounds, including when used as raw material gidrirovannoe fraction With6-C8the pyrolysis condensate fraction containing about 80 wt.% aromatic hydrocarbons. Processing of such fractions of the pyrolysis condensate fraction is required at Russian plants.

The present invention is to increase the growth of aromatic compounds in catalyzate in the processing of pyrolysis condensate fraction, which is characterized by a high content of aromatic compounds and low content of paraffins and naphthenes.

The problem is solved is described by way of aromatization of non-aromatic hydrocarbons contained in gidrirovannoe fraction6-C8/sub> the pyrolysis condensate fraction, which includes the interaction at elevated temperature of the feedstock - gidrirovannoe fraction6-C8the pyrolysis condensate fraction containing not less than 70 wt.% aromatic hydrocarbons and 8-30 wt.% nah, aromatization catalyst is a zeolite with the diameter of the entrance window 5,1-of 7.3 Å, having a molar ratio of silicon to aluminum, equal 25-140 modified with a metal selected from the series: zinc, gallium, copper, silver, rhodium, platinum, rare earth elements and their combination.

Preferably use a zeolite selected from the MFI, BEA, MWW, FAU, MOR - types, and more preferably the MFI zeolite with a molar ratio of silicon to aluminum 25-40.

Used zeolite mainly has the following metals: zinc and/or gallium 0.5 to 6 wt.%, silver 0.5 to 3 wt.%, copper and/or rhodium and/or rare earth element, 0.5-1 wt.%, platinum 0.3 to 1 wt.%.

Communication is usually carried out in a flow reactor with a fixed catalyst bed at 360-520°C, a pressure of 1-50 atmospheres, a feed rate of the raw material of 0.3-12 h-1and when the molar ratio of hydrogen to the hydrocarbon feedstock is (0,3-12):1.

We found that not any zeolite aromatization catalyst suitable for increasing the degree of aromatization of raw materials with high (>70%) content of aromatic compounds in the composition and ponies the military (less than 30%) content of paraffins and naphthenes. We have chosen the catalyst with the characteristics specified in the formula, has an acidic centers with activation energy 115-180 kJ/mol. The claimed technical result is achieved in the volume of the combination of features set out in claim 1 of the formula, and not achieved abroad. We have developed a way of aromatization of hydrocarbons of the claimed composition can be entered into the General technological scheme of processing of pyrolysis condensate fraction this process stage after Hydrotreating, the paraffins and naphthenes, are directly converted into aromatic hydrocarbons without the implementation of additional phases that will lead in General to increase the yield of benzene and reduce the formation of fuel gases.

The following are specific examples of the invention, the results of carrying out the invention are given in table 4.

Example 1.

For the preparation of the catalyst Zn(3)MFI(40) was taken ammonium form of the zeolite of MFI structure with a molar ratio of silicon to aluminum 40, which is then impregnated with an aqueous solution of salt of Zn(NO3)2*6H2O based on 3 weight percent zinc in the catalyst and progulivali at 500°C.

In the notation of the samples in table 4 after metal in parentheses are the mass of the contents, after structural-type zeolite are shown in parentheses molar ratio of cu is mnie to aluminum in it.

Example 2.

Catalytic tests were carried out in flowing steel reactor with a fixed catalyst bed, the reaction products were separarely and analyzed by gas chromatography. The catalyst described in example 1 was preobably in a stream of hydrogen at a temperature of 400°C, then the temperature was increased to 500°C and at pressures of 0.1 MPa with the ratio of hydrogen to the raw material of 1.5:1 was served raw with massive speed 3 g/g*h In the quality of raw material used model blend with the composition (table 1), similar to the distribution of hydrocarbons to gidrirovannoe fraction of the pyrolysis condensate fraction.

Table 1
The composition of the mixture model
Hydrocarbonswt.%
Hexane3,4
Cyclohexane4,2
Heptane3,3
Octane4,2
Benzene34,1
Toluene50,7

Model mixture contained as aromatic uglevodorov the s in the amount of 85 wt.%, and paraffins and naphthenes in the amount of 15 wt.%.

The results of the experiment are presented in table 4, as indicators of the reaction represented by the following calculated values:

The conversion of paraffins and naphthenes:

where malcoholnye- weight paraffins and naphthenes, supplied with the original mixture in the reactor in unit time, malcerreca- weight paraffins and naphthenes interval C6-C8 in the reaction products obtained in units of time.

The growth of aromatic hydrocarbons:

,

where maramesh.- weight of aromatic substances in the mixture supplied in unit time, mentrance- the total mass of hydrocarbon entering the reactor in unit time. Growth benzene rings:

where mi Aromat- mass i aromatic substances from the series of benzene, toluene, xylene, ethylbenzene, and With9and C10+formed in unit time; Mimolecular weight i aromatic substances.

,

where the benzene ringsource- the number of benzene rings in the feedstock.

Examples 3-10.

Similar to example 2, the difference is that changing reaction conditions:

the feed rate of raw materials, the molar ratio of hydrogen to the raw material, temperature and pressure.

Example 11.

The catalyst obtained analogously to example 1, the difference lies in the fact that as a starting zeolite taken ammonium form of the zeolite of the BEA with the ratio of silicon to aluminum 33, which was then impregnated with an aqueous solution of salt Ga(NO3)2*8H2O the rate of 3 wt.% gallium on the weight of the calcined catalyst.

Example 12.

Similar to example 2, the difference is that the used catalyst described in example 11. The result of catalytic experiment are presented in table 4.

Example 13.

The catalyst obtained analogously to example 1, the difference lies in the fact that as a starting zeolite taken the hydrogen form of the zeolite MWW, with the ratio of silicon to aluminum of 30, which was then impregnated with an aqueous solution of salt ((NH3)4Pt)Cl2*4H2O the rate of 1 wt.% platinum on the weight of the calcined catalyst.

Example 14.

Similar to example 2, the difference is that the used catalyst described in example 13. The result of catalytic experiment are presented in table 4.

Example 15.

The catalyst obtained analogously to example 13, the difference is that the amount of salt ((NH3)4Pt)Cl2*4H2O was taken as 0.3 wt.% platinum on the weight of the calcined catalyst.

Example 16.

Similar to example 2, the difference lies in the fact that he used the catalysis of the torus, described in example 15. The result is presented in table 4.

Example 17.

The catalyst obtained analogously to example 1, the difference lies in the fact that as a starting zeolite taken ammonium form of zeolite MFI with the ratio of silicon to aluminum 25, which was then impregnated with an aqueous solution of salt Ga(NO3)2*8H2O the rate of 1.5 wt.% gallium on the weight of the calcined catalyst.

Example 18.

Similar to example 2, the difference is that the used catalyst described in example 17. The result of catalytic experiment are presented in table 4.

Example 19.

Similar to example 17, the difference is that the amount of salt Ga(NO3)2*8H2About was taken from a amount of 6 wt.% gallium on the weight of the calcined catalyst.

Example 20.

Similar to example 2, the difference is that the used catalyst described in example 19. The result of catalytic experiment are presented in table 4.

Example 21.

Similar to example 1, the difference consists in that the molar ratio of silicon to aluminum in the original zeolite is 140.

Example 22.

Similar to example 2, the difference is that the used catalyst described in example 21. The result of catalytic experiment are presented in table 4.

Example 23.

Similar to example 1, the difference is that they say the Noe ratio of silicon to aluminum in the original zeolite is 25, as well as the amount of salt Zn(NO3)2*6N2O was taken as 0.5 wt.% the weight of the calcined catalyst.

Example 24.

Similar to example 2, the difference is that the used catalyst described in example 23. The result of catalytic experiment are presented in table 4.

Example 25.

Analogous to example 23, the difference is that the amount of salt Zn(NO3)2*6N2Oh was taken as 6 wt.% the weight of the calcined catalyst.

Example 26.

Similar to example 2, the difference is that the used catalyst described in example 25. The result of catalytic experiment are presented in table 4.

Example 27.

For the preparation of bimetallic catalyst Zn(2)Ga(3)MFI(40) was taken ammonium form of zeolite MFI with the ratio of silicon to aluminum 40, which is then impregnated with an aqueous solution of salt GA(NO3)2*8H2About the rate of 3 weight percent gallium. The impregnated zeolite was consistently progulivali in a stream of air at 500°C in a stream of hydrogen at 400°C. the thus Obtained catalyst was then modified the second metal zinc by impregnation of the catalyst salt solution of Zn(NO3)2*6N2O the rate of 2 wt.% zinc and calcining in a stream of air at 500°C.

Example 28.

Similar to example 2, the difference is ostoic is he was using the catalyst described in example 27. The result of catalytic experiment are presented in table 4.

Example 29.

Analogous to example 27, the difference lies in the fact that as the second metal modifier used silver. The amount of salt AgNO3was taken from the calculation of 0.5 wt.% silver on the weight of the calcined catalyst.

Example 30.

Similar to example 2, the difference is that the used catalyst described in example 29. The result of catalytic experiment are presented in table 4.

Example 31.

Analogous to example 29, the difference is that the amount of salt AgNO3for inoculation were taken at the rate of 3 wt.% silver on the weight of the calcined catalyst.

Example 32.

Similar to example 2, the difference is that the used catalyst described in example 31. The result of catalytic experiment are presented in table 4.

Example 33.

Analogous to example 27, the difference lies in the fact that as the second metal modifier used copper. The amount of salt C(NO3)2*3H2O was taken from the calculation of 0.5 wt.% copper on the weight of the calcined catalyst.

Example 34.

Similar to example 2, the difference is that the used catalyst described in example 33. The result of catalytic experiment are presented in table 4.

Por the measures 35.

Analogous to example 33, the difference is that the amount of salt C(NO3)2*3H2About for promotion were taken at the rate of 1 wt.% copper on the weight of the calcined catalyst.

Example 36.

Similar to example 2, the difference is that the used catalyst described in example 35. The result of catalytic experiment are presented in table 4.

Example 37.

Analogous to example 27, the difference lies in the fact that as the second metal modifier used rhodium. The amount of salt Rhl3*4H2O took at the rate of 1 wt.% rhodium by weight of the calcined catalyst.

Example 38.

Similar to example 2, the difference is that the used catalyst described in example 37. The result of catalytic experiment are presented in table 4.

Example 39.

Analogous to example 27, the difference lies in the fact that as the second metal modifier used cerium. The amount of salt CE(NO3)2*6N2O took at the rate of 1 wt.% cerium on the weight of the calcined catalyst.

Example 40.

Similar to example 2, the difference is that the used catalyst described in example 39. The result of catalytic experiment are presented in table 4.

Example 41.

Similar to example 2, the difference is that the raw material used gidrirovannoe fracc the Yu 6-C8the pyrolysis condensate fraction, the composition of which is given in table 2.

Table 2
The composition gidrirovannoe fraction6-C8the pyrolysis condensate fraction
Hydrocarbonswt.%
With50,2
With66,9
Cyclohexane0,8
With71,0
With81,5
With90,5
paraffins10+0,6
Benzene53,6
Toluene20,2
Xylenes13,0
Aromatic C91,3
aromatic With10+0,5

The result of catalytic experiment to depict what Allen in table 4.

Example 42.

Similar to example 2, the difference is that the raw material used model mixture containing aromatic hydrocarbons in the amount of 70 mass%, the composition of which is given in table 3.

Table 3
The composition of the mixture model
Hydrocarbonswt.%
Hexane6,0
Cyclohexane8,0
Heptane7,0
Octane9,0
Benzene27,5
Toluene42,1

The result of catalytic experiment are presented in table 4.

Thus, table 4 shows that the claimed technical result is obtained in the scope of the claimed combination of features. We first developed a method of flavoring a fraction of the pyrolysis condensate fraction With6-C8characterized by a high content of aromatic compounds, without additional stages and the introduction of more the positive connections.

1. The way of aromatization of non-aromatic hydrocarbons contained in gidrirovannoe fraction6-C8the pyrolysis condensate fraction, including interaction feedstock with a metal-containing zeolite catalyst for the aromatization at elevated temperature, characterized in that the feedstock used gidrirovannoe fraction With6-C8the pyrolysis condensate fraction containing not less than 70 wt.% aromatic hydrocarbons and 8-30 wt.% nah, but as a catalyst for aromatization use zeolite with the diameter of the entrance window 5,1-of 7.3 Å, having a molar ratio of silicon to aluminum, equal 25-140 modified with a metal selected from the series: zinc, gallium, copper, silver, rhodium, platinum, rare earth elements and their combination.

2. The method according to claim 1, characterized in that the use of zeolite selected from the MFI, BEA, MWW, FAU, MOR-types, more preferably MFI zeolite with a molar ratio of silicon to aluminum 25-40.

3. The method according to claim 1, characterized in that the content of zinc and/or gallium in the zeolite is 0.5-6 wt.%.

4. The method according to claim 3, characterized in that the silver content in the zeolite is 0.5-3 wt.%.

5. The method according to claim 3, characterized in that the copper content, and/or rhodium and/or rare earth element in the zeolite is 0.5-1 wt.%.

6. The method according to claim 1, the tives such as those the content of platinum in the zeolite is 0.3-1 wt.%.

7. The method according to claim 1, characterized in that the interaction is carried out in a flow reactor with a fixed catalyst bed at 360-520°C, a pressure of 1-50 atmospheres, mass flow rate of feed of 0.3-12 h-1and when the molar ratio of hydrogen to the hydrocarbon feedstock is (0,3-12):1.



 

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2 cl, 5 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: alkylbenzol with structure R1R2CH(Ph) is obtained from alkylphenyl alcohol with structure R1R2C(Ph)OH. Method includes following stages: (a) supply of initial flow, containing alkylphenyl alcohol with structure R1R2C(Ph)OH, into reactor with catalytic distillation zone; (b) simultaneously in reactor: (i) contacting of initial flow, containing R1R2C(Ph)OH, with hydrogen in catalytic distillation zone in order to convert R1R2C(Ph)OH into R1R2CH(Ph) and to form reaction mixture and (ii) separation of R1R2CH(Ph) from reaction mixture by fraction distillation in order to obtain higher than catalytic distillation zone, flow, which contains R1R2CH(Ph) with lower concentration of R1R2C(Ph)OH in comparison to initial reactor flow in position higher than catalytic reaction zone; R1 and R2 each represent hydrogen or hydrocarbon group with 1-10 carbon atoms and one of R1 and R2 is not hydrogen.

EFFECT: more pure alkylbenzol with smaller amount of undesirable by-products and using smaller number of stages.

6 cl, 5 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention describes zeolite-containing catalyst for transformation of aliphatic hydrocarbons C2-C12 to a mix of aromatic hydrocarbons or high-octane gasoline component containing zeolite ZSM-5 with silicate module SiO2/Al2O3=60-80 mol/mol and 0.02-0.05 wt % of residual sodium oxide content, zeolite structural element, promoter and binding component, with zirconium or zirconium and nickel oxides as zeolite structural component, and zinc oxide as promoter, at the following component ratio (wt %): zeolite 65.00-80.00; ZrO2 1.59-4.00; NiO 0-1.00; ZnO 0-5.00; Na2O 0.02-0.05, the rest being binding component. Also, a method for obtaining zeolite-containing catalyst is described, which involves mixing reagents, hydrothermal synthesis, flushing, drying and calcinations of sediment. The reaction mix of water solutions of aluminum, zirconium and nickel salts, sodium hydroxide, silicagel and/or aqueous silicate acid, inoculating zeolite crystals with ZSM-5 structure in Na or H-form, and structure-former, such as n-butanol, is placed in an autoclave, where hydrothermal synthesis is performed at 160-190°C for 10-20 hours with continuous stirring; the hydrothermal synthesis over, Na-form pulp of the zeolite is filtered; the obtained sediment is flushed with domestic water and transferred to salt ion exchange by processing by water ammonium chloride solution with heating and stirring of the pulp; the pulp obtained from salt ion exchange is filtered and flushed with demineralised water with residual sodium oxide content of 0.02-0.05 wt % on the basis of dried and calcinated product; flushed sediment of ammonium zeolite form proceeds to zinc promoter introduction and preparation of catalyst mass by mixing of ammonium zeolite form modified by zinc and active aluminum hydroxide; obtained catalyst mass is extruded and granulated; the granules are dried at 100-110°C and calcinated at 550-650°C; calcinated granules of zeolite-containing catalyst are sorted, ready fraction of zeolite-containing catalyst is separated, while the granule fraction under 2.5 mm is milled into homogenous powder and returned to the stage of catalyst mass preparation. The invention also describes method of transformation of aliphatic hydrocarbons to high-octane gasoline component or a mix of aromatic hydrocarbons (variants), involving heating and passing raw material (gasoline oil fraction direct sublimation vapours or gas mix of saturated C2-C4 hydrocarbons) through stationary layer of the aforesaid catalyst.

EFFECT: reduced number of components and synthesis stages of zeolite-containing catalyst; increased transformation degree of raw material; improved quality and yield of target products with the said catalyst.

4 cl, 8 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to petrochemical and chemical industry, particularly a method of preparing moulded catalysts for conversion of methane into aromatic hydrocarbons and hydrogen in nonoxidative conditions. The invention describes a catalyst for a nonoxidative methane conversion process, containing high-silica zeolite H-ZSM-5, a binding additive - calcium form of montmorillonite, modifying elements - molybdenum and cobalt, where content of the binding additive in the catalyst is not more than 40.0 wt %, while content of molybdenum and cobalt is not more than 3.0 wt % and 1.0 wt %, respectively. Described is a method of preparing a catalyst, involving modification of zeolite with promoting elements through successive wetness impregnation of zeolite H-ZSM-5 with molybdenum and cobalt salt solutions, followed by calcination, and then mixing the zeolite modified with metals with a binding additive suspension in a given proportion to obtain a moulding mass and moulding said mass into granules in a moulding device. The invention also describes a method for nonoxidative conversion of methane in the presence of the catalyst described above.

EFFECT: high efficiency of the nonoxidative methane conversion process owing to high activity and stability of the catalyst.

4 cl, 7 ex, 1 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to production of zeolite catalysts, catalysts thus produced and method of producing synthetic fuel using produced catalyst. Proposed methods comprises zeolite two-step loading, impregnating zeolite with cobalt compound in solution and drying in air flow after every loading. Invention covers also catalysts produced by said methods. It covers also the method of producing synthetic fuel using produced catalyst, its activation and synthesis of hydrocarbons, particular, aliphatic hydrocarbons C5-C10 from synthesis gas that represents CO and H2.

EFFECT: higher activity and isomeric selectivity.

36 cl, 2 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: bifunctional cobalt-containing zeolite catalyst for synthesis of aromatic hydrocarbons (mixture of benzene, toluene, xylols and ethyl benzene) from synthetic gas contains a structural promoter - magnesium (II) oxide and an energy promoter - titanium oxide or hafnium oxide, in which the zeolite component used is zeolite ZVM in Ga form with molar ratio SiO2/Al2O3=30, and ratio of components in pts. wt: cobalt 50-150, magnesium (II) oxide 2-8, hafnium oxide or titanium oxide 2-5, zeolite (Ga form) 100-300, a method of preparing said catalyst and a method for synthesis of aromatic hydrocarbons from synthetic gas using said catalyst. The catalyst is characterised by low formation carbon dioxide - main by-product whose output is over 100 g/m3, and optimum ratio of components reaches 50 g/m3. Disclosed catalyst is characterised by high stability and enables synthesis of aromatic hydrocarbons without loss of selectivity for desired synthesis products for a long period of time (over 30 hours).

EFFECT: possibility of selective synthesis of aromatic hydrocarbons with output of desired products.

8 cl, 15 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for converting hydrocarbons, which contains zeolite, method of making said catalyst and method of converting hydrocarbon petroleum products on the catalyst. The zeolite-containing catalyst for converting hydrocarbons, which contains zeolite, heat resistant inorganic oxide and optionally clay, is distinguished by that, the said zeolite has MFI structure, which contains phosphorous and transition metals, or a mixture of said zeolite with MFI structure, containing phosphorous and transition metals, with macroporous zeolite, which contains 75 to 100 wt % of the said zeolite with MFI structure in terms of mass of the mixture, containing phosphorous and transition metals, and 0 to 25 wt % macroporous zeolite; wherein the said zeolite with MFI structure, containing phosphorous and transition metals, in terms of mass of oxide, has the following chemical formula without taking water into account: (0 to 0.3)Na2O·(0.03 to 5.5)Al2O3·(1.0 to 10)P2O5·(0.7 to 15)M1xOy·(0.01 to 5)M2mOn·(0.5 to 10)RE2O3·(70 to 97)SiO2 I or (0 to 0.3)Na2O·(0.3 to 5)Al2O3·(1.0 to 10)P2O5·(0.7 to 15)MpOq·(0.5 to 10)RE2O2·(70 to 98)SiO2 II in which M1 is a transition metal, which is chosen from Fe, Co and Ni, M2 is a transition metal, which is chosen from Zn, Mn, Ga and Sn, M is a transition metal, which is chosen from Fe, Co, Ni, Cu, Zn, Mo or Mn, and RE is a rare-earth metal; x is equal to 1 or 2, where if x equals 1, y equals half the valency of transition metal M1, and when x equals 2, y equals valency of transition metal M1; m equals 1 or 2, when m equals 1, n equals half the valency of transition metal M2, and when m equals 2, n equals valency of transition metal M2; p equals 1 or 2, when p equals 1, q equals half the valency of transition metal M, and when p equals 2, q equals valency of transition metal M; the catalyst also contains an auxiliary component, one or more of which are chosen from a group consisting of IVB group metals, group VIII base metals and rare-earth metals of the period table of elements; in terms of catalyst mass, the said catalyst contains 1 to 60 wt % zeolite, 0.1 to 10 wt % auxiliary component of the catalyst, 5 to 98 wt % heat resistant inorganic oxide and 0 to 70 wt % clay in form of oxides. The method of preparing the catalyst involves mixture and suspension of all or part of the heat resistant inorganic oxide and/or its precursor, water and optionally clay, addition of zeolite and drying the obtained suspension, addition of auxiliary compound before addition of zeolite and before or after addition of clay, addition of acid to establish pH of the suspension equal to 1 to 5, ageing at 30 to 90°C for 0.1 to 10 hours and addition of the remaining heat resistant inorganic oxide and/or its precursor after ageing.

EFFECT: obtained catalyst has high activity and stability and is highly capable of converting petroleum hydrocarbons with high output of propylene, ethylene and lower aromatic hydrocarbons.

20 cl, 24 ex, 5 tbl

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