Method for cyclization of normal alkanes
SUBSTANCE: invention refers to a method for cyclization of normal n-alkanes consisting in the fact that gas and raw material mixture consisting of hydrogen-containing gas and straight-run gasoline fraction boiling away within the range of 85-180°C or C7-C12 synthetic hydrocarbon fraction or C7-C10 individual n-alkane mixture is passed through catalyst layer at temperature of 400-520°C, process pressure of 0.1-3.5 MPa, volume feed rate of the raw material within the range of 0.5-2.54 h-1, ratio of hydrogen-containing gas to the raw material 800:1-1500:1 Nm3/m3 with catalyst containing, wt. %: platinum 0.20-0.85, zeolite KL 40.0-80.0, aluminum oxide - the rest. The catalyst contains zeolite KL crystallite morphology of which corresponds to "short cylinder" type, crystallite size being from 200 to 2000 nm and ratio of crystallite length to diameter being from 0.2:1 to 2:1.
EFFECT: increased catalyst activity and providing the output of stable catalysate of not less than 80 wt % with cyclic hydrocarbon content of not less than 55wt % including C8+ arene content of not less than 63 rel% what allows to qualify it is a component of motor car and aviation gasolines or jet engine fuel.
1 tbl, 3 ex
SUBSTANCE: catalyst contains carrier from porous zeolite KL and binding agent and catalytically active substance - platinum. Carrier additionally contains tin tetrachloride pentahydrate nanopowder, and as binding agent - mixture of gibbsite and rutile powders in equal proportions, with particle size of each not exceeding 40 mcm. Ratio of ingredients is in the following range, wt %: platinum - 0.3-0.8, mixture of gibbsite and rutile powders - 25-70, zeolite KL - 29.12-74.69, tin tetrachloride pentahydrate - 0.01-0.08. Claimed catalyst is characterised by high activity in reactions of aromatisation of synthetic hydrocarbons.
EFFECT: invention also relates to method of obtaining such catalyst.
2 cl, 1 tbl, 4 ex
SUBSTANCE: according to the method, the starting raw material is supplied into two successively connected reaction units - first and second with pentasil ceolite catalyst elements; the reaction units are characterised by the environment for hydrocarbon conversion into aromatic ones; the mixture produced after reaction units are divided into liquid and gas fractions; the gas fraction is supplied into an input of the first and second reaction unit. The gas fraction produced after the reaction units are divided into hydrogen-containing gas and a wide light hydrocarbon fraction containing olefins; the hydrogen-containing gas is supplied into an oxygenate synthesis unit; the formed oxygenated are supplied into an input of the first and second reaction units; the wide light hydrocarbon fraction containing olefins is supplied into an input of the first reaction unit.
EFFECT: using the present invention enables increasing the effectiveness of aromatic hydrocarbon concentrates and the alkyl benzene, particularly xylene, selectivity.
19 cl, 5 dwg, 1 ex
SUBSTANCE: described is catalyst of hydroisomerisation, including zeolite of ZSM-23 type, palladium and aluminium oxide, containing components in the following concentrations, wt %: zeolite of ZSM-23- 50-80, palladium - not more than 0.6; boron 1.0-3.0; Al2O3 - the remaining part, which has pore volume not less than 0.25 cm3/g, specific surface not less than 150 m2/g, average diameter of pores not smaller than 4 nm. Method of catalyst preparation consists in soaking zeolite ZSM-23-containing carrier with boric acid solution with the following drying and calcinations, and further soaking with water solution of palladium nitrate with the following drying and calcinations. Described is process of hydroisomerisation of Diesel fuel, which contains not more than 30 ppm of sulphur, carried out at 320-340°C, pressure 2.5-6.5 MPa, volume rate of raw material supply 2-6 h-1, volume ratio hydrogen/raw material - 200-600 nm3/m3 in presence of catalyst with given above composition.
EFFECT: obtaining catalyst, which makes it possible to carry out process of hydroisomerisation with obtaining Diesel fuels with lower pour point, with high output and cetane number.
12 cl, 2 tbl, 4 ex
SUBSTANCE: invention relates to oil refining, particularly catalysts for hydroisomerisation of oil stock. The disclosed catalyst includes a hydrogenating metal component on a support comprising zeolite and aluminium oxide. The hydrogenating metal component used is base metals Ni, Mo, W or mixtures thereof and noble metals Pd and Ir, and the zeolite is a mixture of medium-pore zeolite TSVN with a pentasil structure and a wide-pore ultrastable zeolite USY. Content of acidic sites in the disclosed catalyst is in the range of 400-600 mcmol/g. The catalyst further contains a boron oxide or phosphorus oxide promoter. The disclosed catalyst has the following ratio of components, wt %: base metals - 7-12, noble metals - 0.1-1.0; zeolite mixture - 60-70; promoter - 0.5-4.0; aluminium oxide - up to 100. The invention also relates to a method for hydroisomerisation of oil stock in the presence of said catalyst.
EFFECT: disclosed catalyst and method for isomerisation of oil stock using said catalyst enable to obtain high-quality winter and arctic grade diesel fuels with high output.
5 cl, 2 tbl, 4 ex
SUBSTANCE: catalyst comprises a support which is prepared using high-silica zeolite KL and boehmite, and the catalytically active substance is both platinum crystallites immobilised on the surface of the catalyst and platinum particles localised inside the zeolite channel, having size of 0.6-1.2 nm. The boehmite particles have a size of no more than 45 mcm. The zeolite particles have size of no more than 0.2 mm. The ingredients are in the following ratios (wt %): platinum - 0.3-0.8; boehmite - 19.9-59.5; zeolite KL - 79.8-39.7. The catalyst may further include an oxide and/or metal promoter selected from: Sn, In, Ir, Re, Ba. The group of inventions also includes methods of producing catalysts, which include preparing a granular support based on zeolite and aluminium hydroxide and depositing platinum on the support.
EFFECT: improved catalyst.
4 cl, 1 tbl, 6 ex
SUBSTANCE: invention deals with two-stage method of obtaining high-octane base gasoline with application of liquid and gaseous hydrocarbon raw material in presence of catalyst, and circulation of nonconverted raw material and hydrocarbon gases. As liquid hydrocarbon raw material used is oil or gas condensate, or their mixture; as gaseous hydrocarbon raw material used is C1-C4 fraction and/or C3-C4 fraction and circulating hydrocarbon gases; liquid hydrocarbon raw material is subjected to fractioning in fractionation column with removal of straight-run fractions with limits of evaporation within the temperature interval C5-75°C, benzene fraction with limits of evaporation within the temperature interval 75-85°C, fraction 85-(160-220)°C and circulating hydrocarbon gases; fraction with limits of evaporation within temperature interval C5-75°C and 85-(160-220)°C are supplied to first stage of contact with zeolite-containing catalyst or system of catalysts, promoted with metals of I-VIII group of Periodic table, benzene fraction with limits of evaporation within the temperature interval 75-85°C is removed from fractionation products. Gaseous hydrocarbon raw material is supplied to second stage of contact; it contacts with zeolite-containing catalyst or system of catalysts, promoted with metals of I-VIII group of Periodic table, and contact in first and second stages takes place with the course of main reactions - isomerisation, aromatisation and hydration, products of contact of first and second stages together undergo stabilisation and fractionation with separation of target product - high-octane base gasoline, evaporating within temperature interval C5-(160-220°C), residue higher than (160-220°C), non-converted raw material, which circulates in first stage raw material, and hydrocarbon gases, which circulate in second stage raw material.
EFFECT: obtaining high-octane base gasoline with improved ecological characteristics.
6 cl, 1 dwg, 2 tbl, 3 ex
SUBSTANCE: invention relates to oil refining and petrochemical industry, particularly to methods of producing catalysts for converting straight-run gasoline to a high-octane gasoline component with low benzene content. Described is a catalyst containing the following, wt %: H-ZSM-5 type high-silica zeolite with silica modulus SiO2/Al2O3 = 30-50 - 94.0-99.0, and a heteropoly compound based on cobalt tungstobismuthate or cobalt tungstophosphate 1.0-6.0, formed during heat treatment. Described is a method of producing a catalyst by mechanochemical treatment of the H form a H-ZSM-5 type high-silica zeolite with silica modulus SiO2/Al2O3=30-50 in a vibrating mill for 0.1-24 hours, moulding the catalyst mass into granules, drying and saturating with chloride solutions of corresponding heteropoly compounds of cobalt tungstobismuthate or cobalt tungstophosphate, followed by drying, and the catalyst is formed during heat treatment at 540-550°C for 0.1-12 hours. Described is a method of converting straight-run gasoline to a high-octane gasoline component in the presence of the described catalyst at 350-425°C, bulk speed of 1.0-2.0 h-1 and pressure of 0.1-1.0 MPa.
EFFECT: obtaining an active and selective catalyst for converting straight-run gasoline to a high-octane gasoline component with low benzene content of not more than 2,0 wt %.
3 cl, 1 tbl, 6 ex
SUBSTANCE: invention relates to oil refining and petrochemical industry, particularly to methods of producing catalysts for converting a straight-run gasoline fraction into a high-octane gasoline component with low benzene content. Described is a catalyst which contains the following, wt %: H-ZSM-5 type high-silica zeolite with silica modulus SiO2/Al2O3 = 30-50 - 94.0-99.0, cobalt molybdo-bismuthate or molybdo-phosphate 1.0-6.0, formed during heat treatment. Described is a method of producing a catalyst, which involves hydrothermal crystallisation of a reaction mixture at 120-180°C, which contains sources of silicon, aluminium and alkali metal oxides, hexamethylenediamine and water, followed by drying and calcining, mechanochemical treatment in a vibration mill, moulding with further saturation of the H-form of the H-ZSM-5 type high-silica zeolite with silica modulus SiO2/AI2O3=30-50 with chloride solutions of corresponding heteropoly compounds: cobalt molybdo-bismuthate or cobalt molybdo-phosphate, as a modifying additive, followed by mechanochemical treatment in a vibration mill for 0.1-24 hours, moulding the catalyst mass into granules, drying and calcining at 540-550°C for 0.1-12 hours. Described is a method of converting a straight-run gasoline fraction into high-octane gasoline component with low benzene content in the presence of the catalyst described above at 350-425°C, volume rate of 1.0-2.0 h-1 and pressure of 0.1-1.0 MPa.
EFFECT: high activity and selectivity of the catalyst.
3 cl, 1 tbl, 7 ex
FIELD: process engineering.
SUBSTANCE: invention relates to petrochemical and oil processing industries. Zeolite-bearing catalyst comprises zeolite ZSM-5 with silicate module SiO2/Al2O3=30-80 mol/mol, and zeolite structure elements, e.g. niobium oxide and/or molybdenum oxide and/or cobalt oxide, or mixes thereof, and zirconium oxide, at the following ratio of components, wt %: zeolite - 70.00-90.0; ZrO2 - 0-3.00; Nb2O3 - 0-3.00; MoO3 - 0-3.00; CoO - 0-2.00; Na2O - 0.03-0.10, and binder making the rest. Proposed method of producing said catalyst comprises mixing reagents, hydrothermal synthesis, washing, drying and calcination of precipitate. Note here that reaction mix produced by mixing water solutions of aluminium nitrate, sodium hydroxide, silicic acid or KCKG silica gel, niobium pentachloride, zirconium sulphate, molybdenum trioxide, zeolite seed crystals with ZSM-5/MF1 structure in amendment Na- or H-form, for example, butanol-1, monoethanolamine, dibutylamine, diethylentriamine, is loaded into reactor for hydrothermal synthesis at 175-185°C for 8-24 h. Thereafter, pulp of Na-form zeolite is filtered. Obtained precipitate is repulped in water solution of sodium oxide hydrate. Zeolite precipitate is filtered and repulped in water solution of ammonia bicarbonate. Zeolite precipitate is filtered and directed for acid or salt ion exchange by treatment with nitric acid water solution or water solutions of ammonia salts at pulp heating and mixing. Ammonia bicarbonate is added to pulp obtained after said acid or salt ion exchange and filtered out. Washed H- or NH4-zeolite is dried and subjected to preparation of catalyst mass by mixing zeolite powder with active aluminium hydroxide and concentrated nitric acid. Produced catalyst mass is extruded and pelletised. Produced pellets are dried at 150°C and calcined at 550-600°C. Proposed method of converting virgin gasoline fractions into high-octane gasoline with the help of zeolite-bearing catalyst comprises forcing vapors of virgin gasoline fractions through stationary bed of above described catalyst with additional feed of hydrogen into reaction zone.
EFFECT: higher quality and increased yield.
4 cl, 9 tbl, 21 ex
SUBSTANCE: invention relates to oil-refining and petrochemical industry and production of catalysts used in conversion of C2-C12 aliphatic hydrocarbons and methanol to high-octane gasoline and aromatic hydrocarbons. Described is a zeolite-containing catalyst for converting C2-C12 aliphatic hydrocarbons and methanol to high-octane gasoline and aromatic hydrocarbons, which contains zeolite ZSM-5 with silica modulus SiO2/Al2O3=40-100 mol/mol and residual content of sodium oxide of 0.02-0.04 wt %, zeolite structural units and a binding component, wherein the zeolite structural units of the catalyst are niobium oxide and iron oxide or a mixture of oxides of said metals and zirconium oxide, and chromium oxide, with the following content of components (wt %): zeolite 65.00-85.00; ZrO2 0-3,00; Nb2O5 0-0.50; Fe2O3 0-1.00; Cr2O3 0-3.00; Na2O 0.02-0.04; binding component - the balance. Described is a method for obtaining a zeolite-containing catalyst, which involves mixing reactants, hydrothermal synthesis, washing, drying and calcining the residue. The reaction mixture obtained by mixing aqueous salt solutions of aluminium, zirconium, niobium, iron, chromium and sodium hydroxide, silica gel, zirconium sulphate, niobium pentachloride, inoculating zeolite crystals with a ZSM-5 structure in Na- or H-form, a structure-forming agent, for example diethylene triamine (bis-(2aminoethyl)amine) is fed into an autoclave, where hydrothermal synthesis is carried out at 160-190°C for 20-80 hours with constant stirring; at the end of hydrothermal synthesis, Na-form pulp of the zeolite is filtered; the obtained residue is washed with tap water and taken for salt ion exchange by treatment with aqueous ammonium chloride solution while heating and stirring the pulp; the pulp obtained from salt ion exchange is filtered, washed with tap water and then washed with dimineralised water to residual sodium oxide content of 0.02-0.04 wt % with respect to the dried and calcined product; the washed residue of the ammonium zeolite form is taken for preparation of the catalyst mass by mixing the ammonium zeolite form with active aluminium hydroxide; the obtained catalyst mass is extruded and granulated; the granules are dried at 100-110°C and calcined at 550-650°C; the calcined granules of the zeolite-containing catalyst are sorted; the fraction of the finished zeolite-containing catalyst is separated, and the fraction of granules smaller than 2.5 mm is ground into homogenous powder and returned to the step of preparing the catalyst mass. Described also is a method of converting C2-C12 aliphatic hydrocarbons and methanol to high-octane gasoline and aromatic hydrocarbons, which involves heating and passing material - vapour of straight-run gasoline fraction of oil or methanol through a fixed bed of the catalyst described above.
EFFECT: achieving high phase purity of the zeolite catalyst and wide distribution of acid sites thereof according to strength, introduction of more than one modifying element into the zeolite structure, high quality and output of end products on the disclosed catalyst.
4 cl, 9 tbl, 15 ex
SUBSTANCE: invention relates to the application of a catalyst, which contains a monolith and a layer of the catalyst, for the dehydrogenation of alkanes to alkenes or aromatisation in dehydrogenation. The monolith consists of a catalytically inert material with BET surface area <10 m2/g, with the catalyst layer, applied on the monolith, containing platinum and tin and/or rhenium and if necessary other metals on an oxide carrier material, the catalyst layer thickness constitutes from 5 to 500 microns. In addition, the hour volume rate of gas supply constitutes from 500 to 2000 h-1. The invention also relates to methods of the dehydrogenation of alkanes to alkenes and aromatisation in dehydrogenation with the application of the catalyst described above.
EFFECT: claimed application of the catalyst provides high conversions, volume productivity and selectivity.
14 cl, 13 tbl, 25 ex
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
FIELD: process engineering.
SUBSTANCE: invention relates to method of producing aromatic hydrocarbon compounds from light hydrocarbons by catalytic reaction of ring formation and to catalyst to this end. Zeolite-containing compacted catalyst, to be used in method of producing aromatic hydrocarbon compounds from light hydrocarbons by catalytic reaction of ring formation, wherein zeolite contained in zeolite-containing compacted catalyst meets the following requirements: (a) zeolite represents that with average diametre of pores varying from 5 to 6.5 Å; (b) zeolite features diametre of primary particle varying from 0.02 to 0.25 mcm; and (c) zeolite comprises at least one metal element selected from the group consisting of metals from IB-group of periodic system in the form of appropriate cations, and wherein zeolite-containing compacted catalyst comprises at least one element selected from the group made up of elements that belong in IB, IIB, IIIB, VIII groups of periodic system.
EFFECT: lower carburisation and reactivation of catalyst.
6 cl, 4 ex, 6 tbl, 5 dwg
SUBSTANCE: invention relates to technology of making nanostructured metal-carbon composite materials and can be used in heterogeneous and electrocatalysis. The metal-carbon nanocomposite contains metallic nanoparticles of alloys of Pt with a metal selected from Ru, Re, Rh, uniformly dispersed in the carbon matrix structure. The matrix is made from polyacrylonitrole which is pyrolysed through exposure to infrared light with intensity which corresponds to temperature of 650-1100°C. Total amount of metal equals 0.1-20% of the mass of the composite. The method of making a metal-carbon composite is based on reducing the said metals from solutions of their salts. A combined solution of metal salts, one of which is platinum and the other is either Ru or Re or Rh in an amide or sulfoxide solvent is added to polyacrylonitrile solution in the same solvent and undergoes pyrolysis while exposed to infrared light with intensity which corresponds to temperature of 650-1100°C.
EFFECT: obtained metal-carbon nanocomposites are active in a range of catalytic chemical conversions and can be used as heterogeneous catalysts, eg in dehydration of hydrocarbons and particularly dehydration of cyclohexane.
3 cl, 3 dwg, 11 ex, 3 tbl
FIELD: petrochemical processes and catalysts.
SUBSTANCE: invention relates to processes for hydrocarbon feedstock conversion into aromatic hydrocarbons, in particular to light hydrocarbon aromatization process catalysts, to catalyst preparation processes, and aromatic hydrocarbon production processes. A composite light hydrocarbon aromatization process catalyst is described, which contains acidic microporous component with pore size at least 5 Å and oxide component exhibiting dehydrogenation activity and selected from aluminum hydroxide and/or oxide having transportation pore size at least 20 nm, said oxide component having been treated with promoter element compounds. Described are this catalyst preparation method and aromatic compound production process in presence of above-described catalyst.
EFFECT: increased activity and selectivity regarding formation of aromatic hydrocarbons and stabilized functioning of catalyst.
11 cl, 1 tbl, 23 ex
SUBSTANCE: invention relates to method of dehydration of alkanes with balancing product composition. Gaseous flow of substance, which contains alkanes, is passed in continuous mode through catalyst layer, located in from two to 10 successfully connected reactors of adiabatic, allothermic or isothermic type or in their combination, which results in formation of gaseous flow, containing olefin, hydrogen and alkane which has not reacted, with at least one reactor being adiabatic one, which oxygen is supplied to. At least one of the process parameters: temperature, pressure or ratio of vapour and hydrocarbons is registered in one or more points on at least one of reactors in form of measured values, at least one of the process parameters is purposefully controlled and subjected to impact so that composition of produced gas at output of at least one of reactors remains constant during operation time. Invention also relates to application of said method for dehydration of particular hydrocarbons.
EFFECT: application of claimed method makes it possible to obtain product with constant composition at the output from reactor during the entire operation time.
15 cl, 1 tbl, 5 ex, 8 dwg
SUBSTANCE: method includes: feeding a stream of hydrocarbon feed stock into a hydrogenation/dehydrogenation reactor system to generate a first stream; feeding the first stream into a fractionation apparatus to generate an upper stream containing C7 and lighter paraffins and a lower stream containing heavier paraffins; and feeding said upper stream into a high-temperature reforming reactor system to generate a reforming product stream, where the high-temperature reforming reactor system operates at temperature in the range of 540°C to 580°C.
EFFECT: use of the method reduces power requirements when producing aromatic compounds.
10 cl, 1 dwg