Production method of high-octane gasoline fractions and aromatic hydrocarbons

FIELD: chemistry.

SUBSTANCE: invention refers to production method of high-octane gasoline fractions and/or aromatic hydrocarbons C6-C10 as follows, hydrocarbon materials is heated, evaporated and overheated to process temperature, thereafter providing its contact at temperature 320-480°C and excess pressure with periodically recyclable catalyst containing zeolite of composition ZSM-5 or ZSM-11. Then it is cooled. Contact products are partially condensed, separated into gaseous and liquid fractions by separation. Liquid products of separation are supplied as power primarily to the first distillation column for separation of hydrocarbon gases and liquid stable fraction. The latter is supplied to the second distillation column for separation of high-octane gasoline fraction, or aromatic hydrocarbon fraction, and heavy charge fraction. Gaseous fraction resulted from separation of contact products is supplied to the first distillation column, specifically to intermediate section between infeed and external reflux inlet. External reflux is liquid distillate of the first distillation column.

EFFECT: reduction of power inputs, i.e. quantities of heat and cooling agent, required for reaction products separation.

5 cl, 2 ex

 

The present invention relates to methods of producing high-octane gasoline fractions and/or aromatic hydrocarbons With6-C10of hydrocarbon naphtha fractions.

High octane gasoline is usually obtained by compounding virgin and secondary gasoline with a high octane components (including aromatic hydrocarbons), obtained by different refining processes [Gureev A.A., Zhorov, Y.M., Smidovich EV Production of high-octane gasoline. - M.: Chemistry, 1981, - 224 C.]. Therefore, in General, the technology of obtaining trademark high-octane gasoline is quite complex.

Recently intensively develop new processes and catalysts based on zeolites of the family pentasil, allowing for processing of hydrocarbon raw materials wide fractional composition (from hydrocarbons With5to C12and above) in the high-octane gasoline for one stage. So, for example, known methods for producing high-octane gasoline fractions and/or aromatic hydrocarbons With6-C10[path No. 2163624, CL With 35/095, 50/00, 3/00; SS 1/20, 01J 29/46, 2001; path No. 2186089, CL 10G 35/095, 01J 29/46, 2002; No. 2208624, CL 10G 35/095, 01J 29/46, 2003; U.S. Pat. Of the Russian Federation No. 2221643, CL 01J 29/48, 37/00, 37/10; 10G 35/095, SS 15/02, 2004]. According to the methods of high-octane gasoline fraction and/or aromatic hydrocarbons With -C10derived from hydrocarbon, C2-C12and/or oxygen-containing organic compounds by contacting the feedstock in the temperature range calculated 240-480°and a pressure of 0.1-4.0 MPa with a zeolite-containing catalyst and subsequent cooling and separation of the products of contacting a gaseous fraction and a liquid fraction. As the active component of the catalyst used zeolite pentasil with the structure of ZSM-5 or ZSM-11; may use catalysts modified with items I-VIII groups.

A method of obtaining high-octane gasoline and aromatic hydrocarbons from gas condensate [U.S. Pat. Of the Russian Federation No. 2078791, CL 10G 35/095, 1997]. In this way, hydrocarbons stable gas condensate is subjected to rectification with the release of a number of factions, including light gasoline fraction Nicholas -58°and gasoline fractions 58°-(140-195)°C. Gasoline fraction 58°-(140-195)°are contacting at a temperature of 300-500°and the excessive pressure with a zeolite-containing catalyst prepared on the basis of Pancasila. The reaction products are cooled and separated by separation, stabilization and rectification with the release of hydrocarbon gases C1-C4the propane-butane fraction, a gasoline fraction and a heavy residual fraction. Isolated from the reaction products gasoline faction is compounding with a light gasoline fraction Nicholas -58°With sales of gasoline or sent to the extractive distillation for separation of aromatic hydrocarbons From7-C9.

Known device and method of catalytic high octane gasoline fractions and aromatic hydrocarbons [U.S. Pat. Of the Russian Federation No. 2098173, CL 01J 19/00; 10G 35/04, 3/00; SS 2/12, 1997]. According to the present method of obtaining high-octane gasoline fractions and aromatic hydrocarbons With6-C10of organic materials on the basis of hydrocarbons and/or oxygen-containing compounds is as follows. Raw materials under the excessive pressure is heated, evaporated and overheat to a temperature 340-480°and then at this temperature, is subjected to contacting with the stationary layer is periodically regenerated zeolite catalyst. The reaction products are cooled, condensed and separated in the separator with the release of hydrocarbon gases and liquid catalyzate. Liquid catalysate is sent to distillation column stabilizer, where the removal of dissolved gases. The bottom of the column divert produce stable, which sent the 2nd distillation column, where the selection of high-octane gasoline (FR. <205° (C) and residual fraction (FR. >185°).

The closest in technical essence and the achieved effect is KTU is a method of obtaining high-octane gasoline, implemented on dedicated catalytic installing the [U.S. Pat. Of the Russian Federation No. 2053013, CL 01J 8/06, 10G 35/04, 1996]. According to the selected prototype production of high octane gasoline from a hydrocarbon or oxygen-containing compounds is carried out in two parallel reactor-thermal units, in which there is an alternation of stages of production of gasoline and stages of catalyst regeneration. In particular, obtaining high-octane gasoline from a pre-allocated from the gas condensate or oil straight-run (low-octane) gasoline fraction is as follows.

Straight-run gasoline fraction at a pressure of heat, then evaporated and overheat to a temperature of processing. Overheated raw material is subjected to contact with a stationary layer periodically regenerated zeolite catalyst at a pressure and temperature 320-480°C. the reaction Products are cooled and condensed in heat exchange apparatus and separated in the separator with the release of hydrocarbon gases and liquid unstable catalyzate. Unstable catalysate is heated to 120°and served in the distillation column stabilizer where it stabilized - removal of dissolved gases. The bottom of the column-stabilizer assign stable catalysate which is sent in the 2nd rect Picatinny column, where the separation top of the column of high-octane gasoline (FR. <205° (C) and the cube of the column - residual fractions (FR. >160°).

Periodically carry out regeneration of the catalyst, which is to regulate the burning of the regenerating gas with a certain amount of oxygen and at a temperature of 500-550°With coke deposits formed on the catalyst surface during processing.

In the prototype described the use of catalysts containing zeolites with structure of ZSM-5 and ZSM-11, including modified La.

The main disadvantage of the above methods, their analogs and prototypes are increased energy consumption - heat and refrigerant required for separation of the reaction products.

The problem solved by the present invention is the reduction of energy consumption - the amount of heat and refrigerant required for separation of the reaction products.

The problem is solved in that the receipt of high-octane gasoline fractions and/or aromatic hydrocarbons With6-C10of hydrocarbons carried by heating, evaporation and superheat temperatures of processing, then contacting at a temperature of 320-480°and excessive pressure periodically regenerated catalyst containing a zeolite with structure of ZSM-5 or ZSM-11, the placenta is the accelerated cooling and partial condensation products contact, their separation into gas and liquid fractions by separation, flow of the liquid product separation, nutrition, initially in the first distillation column for separation of hydrocarbon gases and liquid stable fraction and feeding the latter into a second distillation column for separation of high-octane gasoline fraction or fractions of aromatic hydrocarbons and a heavy fraction residue, and supply the selected gaseous fraction separation in the first distillation column at an intermediate section between the input power and the input of cold irrigation, while cold irrigation is a liquid distillate of the first distillation column.

Possible implementation of the separation products of the contacting at a temperature 45-140°C. Possible the implementation stage contacting of the feedstock with the catalyst at a pressure of 0.4-4.0 MPa. Possible regeneration of the catalyst at a temperature of 350-550°and a pressure of 0.1-4 MPa initially regenerating gas with an oxygen content of 0.1-5% vol., and then with oxygen 7-21% about. It is possible that the regenerating gas is produced by mixing part of the exhaust gas regeneration with air or with air and nitrogen.

The main distinctive features of the proposed method are:

the gaseous fraction, isolated by separation and the product contact, in the first distillation column, in the intermediate section between the input power and the input of cold irrigation;

- getting regenerating gas by mixing part of the exhaust gas regeneration with air or with air and nitrogen.

The main advantages of the proposed method are: 1 - reducing energy consumption - the amount of heat and refrigerant required for separation of the reaction products; 2 - increase the yield of gasoline fraction.

Achieved results related to the fact that at the stage of cooling of the reaction products cooling flow not perform to the minimum temperature (usually up to 25-45°With, in the prototype - to 45° (C)providing the maximum condensation of hydrocarbons, and to a higher temperature (up to 140°C), which reduces the required quantity of refrigerant. The reduction of the same amount of heat required for the separation of the reaction products, in particular to provide heat to the process of rectification in the first column, is due to the fact that the power of the column (flow liquid products contact) has a higher temperature.

In addition, by supplying gaseous fraction separation products contact in the intermediate section between the input power and the input of cold irrigation of the first distillation column is additionally the extraction from the gas phase neskondensirovannyh at the stage of primary separation of hydrocarbon, C 5-C7that leads to a slight increase in the yield of gasoline fraction.

The method is as follows. The raw material is preheated to a temperature of the processing in the respective processing units (heat exchangers, furnaces and the like) and in the reactor(s) at a temperature of 320-480°C, a pressure of 0.4-4.0 MPa (preferably from 1.0 to 2.0 MPa) and mass feed rate of the raw material up to 10 h-1subjected to contacting with a zeolite-containing catalyst. Can be used in different types of reactor systems with stationary or moving, or fluidized bed of catalyst. As the zeolite-containing catalyst used in the system, including modified items I-VIII groups or their compounds and prepared according to known methods.

The reaction products (food contact) is cooled in the respective process apparatuses (recuperative heat exchangers) to a temperature 45-140°With (preferably 60-120°) and at this temperature, is subjected to separation with separation of gaseous and liquid fractions. The gaseous fraction is then fed to the first distillation column (column-stabilizer), in an intermediate section between the input power and the input of cold irrigation, and the liquid fraction is served (possibly with additional heating) in the same column as the supply.

Riding stabilization to the pubic selected light fraction, which is cool and share in the corresponding process equipment with the release of hydrocarbon gases With1-C4and liquid distillate, which is returned to the column in the form of cold irrigation (possibly resulting liquefied gas With3-C4). Cube stabilizer selected stable catalysate, part of which is heated in the corresponding process equipment (furnace, boiler and so on) to the working temperature and return to the column stabilizer to maintain the heat balance of the column, and the carrying portion of the cubic product serves (possibly with additional heating) in the second distillation column.

In the second distillation column separates the stable catalyzate emitting top of the column is high-octane gasoline fraction or fractions of aromatic hydrocarbons With6-C10and cube column - residual fractions, wikipeida above 185-205°C.

Regeneration of the catalyst is carried out at a temperature of 350-550°and a pressure of 0.1-4.0 MPa initially regenerating gas with an oxygen content of 0.1-5% vol., and then, as the combustion of the main part of coke with oxygen 7-21% about. Regenerating gas is produced by mixing air with nitrogen. You may receive the regenerating gas by mixing parts from Botanik gas recovery, supplied to the recirculation with air or with air and nitrogen.

The essence of the proposed method and its practical applicability is illustrated by the following examples. Example 1 is similar to prototype and is provided for comparison with the proposed method under the same conditions, example 2 - the proposed method.

Example 1. As raw materials use of straight-run gasoline fraction with PTS=62 MM, having the following size distribution, °S: NK - 36; 10% about., - 61, 50% - 101, 90% - 171, KK - 203 and containing hydrocarbons, wt.%: With3-0,1; C4-3,9; C5-10,2; C6-19,7; C7-26,1; C8-20,7; C9-11,1; C10+-8,2, including n-paraffins to 29.8, ISO and naphthenes - 60,9, aromatic - 9,3.

Raw materials in quantities of 10 t/h at a pressure pre-heated, evaporated, overheat to a temperature of the processing and at a temperature of 350°C, a pressure of 1.5 MPa and a mass flow rate of feed of 1.5 h-1subjected to contact with periodically regenerated catalyst containing 30% wt. Al2About3and 70% of the zeolite with structure of ZSM-5 modified with 0.2% La.

The reaction products (food contact) is cooled from a temperature of 350°With temperatures of 45°With; however, the cost of cooling to 10 t/h flow products are 10038 MJ/h the Cooled product stream contacting at a pressure of 1.41 MPa-rayed at the t separation with separation and 9,54 t/h of liquid unstable catalyzate and 0.46 t/h gaseous fraction 1-C4(4,6% wt.), a byproduct.

Unstable catalysate is heated to a temperature of 120°C, low 2450 MJ/h, and in the quality of food served in the distillation column stabilizer with reflux condenser and reboiler.

The stabilization column has 16 theoretical plates, the plate power supply - 8, reflux number is 1.5; the pressure in the top of the column is to 1.15 MPa, in the cube - 1,18 MPa; the temperature of the top of the column - 54°, cube - 151°, irrigation - 45°S, hot jet - 181°C.

With a dephlegmator column-stabilizer selected 2,82 t/h of hydrocarbon gases With3-C4(28,2%), which is a by-product. Cube column select 6,72 t/h stable catalyzate, having a vapour pressure of 80 kPa.

To support the process of rectification in the column-stabilizer spend: 1 - to supply heat to the reboiler of the column - 2026 MJ/h; 2 - cooling water in the reflux condenser of the column - 1611 MJ/h

The selected cube stabilizer produce stable after discharge pressure up to 0.2 MPa is heated from a temperature of 123 to 200°C, low 2160 MJ/h, and in the quality of food served in a distillation column equipped with a condenser and a reboiler.

Distillation column has 14 theoretical plates, the plate power supply - 7, reflux number to 1.0; the pressure in vercollone - 0.15 MPa, in the cube - 0,18 MPa; the temperature of the top of the column - 139°, cube - 254°, irrigation - 59°S, hot jet - 268°C.

Top of the distillation column select 6,50 t/h (65,0% wt.) gasoline fraction containing 8.7% of wt. hydrocarbons With3-C4, 5.9% of n-paraffins With5+, 41,0% isoparaffins and naphthenes With5+and 44.4% of aromatic hydrocarbons With6-C10, which is the target product is high - octane gasoline AI-95 winter. Cube column select 0,22 t/h (2,2%) heavy fraction of aromatic hydrocarbons, wikipeida above 200°and which is a by-product.

To support the process of distillation in a distillation column spend: 1 - to supply heat to the reboiler of the column - 2160 MJ/h; 2 - cooling water in the reflux condenser of the column - 6368 MJ/h For dobrazhivaniya gasoline to a temperature of 45°spend 182 MJ/h, the cooling of the cubic product columns to 45°S - 114 MJ/h

In General, when processing 10 t/h raw material costs of heat on the processes of distillation of the reaction products (for heating power and heating boilers columns) and are 4476 MJ/h for stabilization of the column, and 4512 MJ/h for distillation columns. The cost of cooling flows are: reaction products (before separation) - 10038 MJ/h; top products stabilizer - 1611 MJ/h, the product is the distillation columns - 6664 MJ/h Total heat input to the rectification by separation of the reaction products are 8988 MJ/h, the cost of cooling all the threads - 18313 MJ/h

Periodically carry out regeneration of the catalyst, which consists in burning the formed catalyst coke deposits regenerating gas with a specific oxygen content.

Example 2. As raw materials use of straight-run gasoline fraction with PTS=62 MM, having the following size distribution, °S: NK - 36; 10% about. - 61, 50% - 101, 90% - 171, KK - 203 and containing hydrocarbons, wt.%: With3- 0,1; C4- 3,9; C5- 10,2; C6- 19,7; C7- 26,1; C8- 20,7; C9- 11,1; C10+- 8,2, including n-paraffins to 29.8, ISO and naphthenes - 60,9, aromatic - 9,3.

Raw materials in quantities of 10 t/h at a pressure pre-heated, evaporated, overheat to a temperature of the processing and at a temperature of 350°C, a pressure of 1.5 MPa and a mass flow rate of feed of 1.5 h-1subjected to contact with periodically regenerated catalyst containing 30% wt. Al2O3and 70% of the zeolite with structure of ZSM-5 modified with 0.2% La.

The reaction products are cooled from a temperature of 350°With temperatures of 100°With; however, the cost of cooling to 10 t/h flow products are 8121 MJ/h Cooled to 100°With the flow of products contact when Yes is the population of 1.41 MPa is subjected to separation with separation and of 7.23 t/h of liquid fraction and 2.77 t/h of gaseous fractions. The liquid fraction is heated to a temperature of 120°C, low 452 MJ/h, and serves as a power in the distillation column stabilizer equipped with a reflux condenser and a reboiler, and a gaseous fraction served in the same column in the intermediate section between the input power and the input of cold irrigation.

The stabilization column has 16 theoretical plates, the plate power supply - 8, the plate entering the gas phase - 5, reflux number is 1.5; the pressure in the top of the column is to 1.15 MPa, in the cube - 1,18 MPa; the temperature of the top of the column - 52°, cube - 148°, irrigation - 40°S, hot jet - 180°C.

With a dephlegmator column-stabilizer selected 3,21 t/h of hydrocarbon gases C1-C4(32,1%), which is a by-product. Cube column select 6,79 t/h stable catalyzate, having a vapour pressure of 80 kPa.

To support the process of rectification in the column-stabilizer spend: 1 - to supply heat to the reboiler of the column - 2512 MJ/h; 2 - cooling water in the reflux condenser of the column - 1897 MJ/h

The selected cube stabilizer produce stable after discharge pressure up to 0.2 MPa is heated temperature 122°to 200°C, low 2202 MJ/h, and in the quality of food served in a distillation column equipped with a condenser and a reboiler.

Distillation columns is and has 14 theoretical plates, plate power - 7, reflux number to 1.0; the pressure in the top of the column - 0.15 MPa, in the cube - 0,18 MPa; the temperature of the top of the column - 139°, cube - 254°, irrigation - 59°S, hot jet - 267°C.

Top of the distillation column select 6,57 t/h (65,7% wt.) gasoline fraction containing 9.2% of wt. butane, 5.9% of n-paraffins With5+and 40.8% isoparaffins and naphthenes C5+and 44.1% of aromatic hydrocarbons With6-C10(including6- 1,6; C7to 12.0; C8- 18,2; C9- 8,7 and C10- 3,6), which is the target product is high - octane gasoline AI-95 winter. Cube column select 0,22 t/h (2,2%) heavy fraction of aromatic hydrocarbons, wikipeida above 200°and which is a by-product.

To support the process of distillation in a distillation column spend: 1 - to supply heat to the reboiler of the column - 2364 MJ/h; 2 - cooling water in the reflux condenser of the column - 6427 MJ/h For dobrazhivaniya gasoline to a temperature of 45°spend 185 MJ/h, the cooling of the cubic product columns to 45°S - 114 MJ/h

In General, when processing 10 t/h raw material costs of heat on the processes of distillation of the reaction products (for heating power and heating boilers columns) and make 2964 MJ/h for stabilization of the column, and 4566 MJ/h for distillation columns. The cost of cooling flows SOS is ablaut: reaction products (before separation) - 8121 MJ/h; top products stabilizer - 1861 MJ/h, the products of distillation columns - 6726 MJ/h Total heat input to the rectification by separation of the reaction products are 7530 MJ/h, the cost of cooling all the threads - 16708 MJ/h

Regeneration of the catalyst is carried out at a pressure of 1.5 MPa initially at a temperature of 500°by submitting a regenerating gas with an oxygen content of 1.0% vol., and after burnout of the main part of catalyst coke at a temperature of 520°and the oxygen content of 20%. Regenerating gas is produced by mixing part of the exhaust gas regeneration supplied to the recirculation, air and nitrogen.

1. Method of producing high octane gasoline fractions and/or aromatic hydrocarbons With6-C10of hydrocarbons by heating, evaporation and superheat temperatures of processing, then contacting at a temperature of 320-480°and excessive pressure periodically regenerated catalyst containing a zeolite with structure of ZSM-5 or ZSM-11, subsequent cooling and partial condensation products contact, their separation into gas and liquid fractions by separation, flow of the liquid product separation as the power is initially in a first distillation column to highlight Ugledar is the breaking gases and liquid stable fraction and feeding the latter into a second distillation column for separation of high-octane gasoline fraction or fractions of aromatic hydrocarbons and fraction of heavy residue, characterized in that the gaseous fraction obtained in the separation products contact, fed to the first distillation column at an intermediate section between the input power and the input of cold irrigation, while cold irrigation is a liquid distillate of the first distillation column.

2. The method according to claim 1, characterized in that the separation of the products of the contacting is carried out at a temperature 45-140°C.

3. The method according to claim 1 or 2, characterized in that the stage of contacting the feedstock with the catalyst is carried out at a pressure of 0.4-4.0 MPa and mass feed rate of the raw material up to 10 h-1.

4. The method according to claim 1, characterized in that the regeneration of the catalyst is carried out at a temperature of 350-550°and a pressure of 0.1-4 MPa initially regenerating gas with an oxygen content of 0.1-5 vol.%, and then with oxygen 7-21%vol.

5. The method according to claim 4, characterized in that the regenerating gas is produced by mixing part of the exhaust gas regeneration with air or with air and nitrogen.



 

Same patents:

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: zeolite catalyst for process of conversion of straight-run gasoline to high-octane number component is described. The said catalyst contains high-silica zeolite with SiO2/Al2O3=60 and residual content of Na2О of 0.02 wt.% maximum, metal-modified, Pt, Ni, Zn or Fe metals being in nanopowder form. Content of the said metals in the catalyst is 1.5 wt.% maximum. Method to manufacture zeolite catalyst for conversion of straight-run gasoline to high-octane number component is described. The said method implies metal modification of zeolite, Pt, Ni, Zn or Fe metals being added to zeolite as nanopowders, produced by electric explosion of metal wire in argon, by dry pebble mixing in air at room temperature. Method to convert straight-run gasoline using the said catalyst is also described.

EFFECT: increase in catalyst activity and gasoline octane number, accompanied by increase in yield.

4 cl, 3 tbl, 4 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention provides isodewaxing catalyst for petroleum fractions containing supported platinum and modifiers wherein supporting carrier is fine powdered high-purity alumina mixed with zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40 at following proportions of components, wt %: platinum 0.15-0.60, alumina 58.61-89.43, zeolite 5-40, tungsten oxide (modifier) 1-4, and indium oxide (modifier) 0.24-0.97. Preparation of catalyst comprises preparing carrier using method of competitive impregnation from common solution of platinum-hydrochloric, acetic, and hydrochloric acids followed by drying and calcinations, wherein carrier is prepared by gelation of fine powdered high-purity alumina with the aid of 3-15% nitric acid solution followed by consecutive addition of silicotungstenic acid solution and indium chloride solution, and then zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40.

EFFECT: increased yield of isoparaffin hydrocarbons.

7 cl, 2 tbl, 7 ex

FIELD: petrochemical processes.

SUBSTANCE: group of inventions relates to processing of hydrocarbon feedstock having dry point from 140 to 400°C and is intended for production of fuel fractions (gasoline, kerosene, and/or diesel) on solid catalysts. In first embodiment of invention, processing involves bringing feedstock into contact with regenerable catalyst at 250-500°C, pressure 0.1-4 MPa, and feedstock weight supply rate up to 10 h-1, said catalyst containing (i) crystalline silicate or ZSM-5 or ZSM-14-type zeolite having general empiric formula: (0.02-0.35)Na2O-E2O3-(27-300)SiO2-kH2O), where E represents at least one element from the series: Al, Ga, B, and Fe and k is coefficient corresponding to water capacity; or (ii) silicate or identically composed zeolite and at least one group I-VIII element and/or compound thereof in amount 0.001 to 10.0 % by weight. Reaction product is separated after cooling through simple separation and/or rectification into fractions: hydrocarbon gas, gasoline, kerosene, and/or diesel fractions, after which catalyst is regenerated by oxygen-containing gas at 350-600°C and pressure 0.1-4 MPa. Hydrocarbon feedstock utilized comprises (i) long hydrocarbon fraction boiling away up to 400°C and composed, in particular, of isoparaffins and naphtenes in summary amount 54-58.1%, aromatic hydrocarbons in amount 8.4-12.7%, and n-paraffins in balancing amount; or (ii) long hydrocarbon fraction boiling away up to 400°C and composed, in particular, of following fractions, °C: 43-195, 151-267, 130-364, 168-345, 26-264, 144-272. In second embodiment, feedstock boiling away up to 400°C is processed in presence of hydrogen at H2/hydrocarbons molar ratio between 0.1 and 10 by bringing feedstock into contact with regenerable catalyst at 250-500°C, elevated pressure, and feedstock weight supply rate up to 10 h-1, said catalyst containing zeolite having structure ZSM-12, and/or beta, and/or omega, and/or zeolite L. and/or mordenite, and/or crystalline elemento-aluminophosphate and at least one group I-VIII element and/or compound thereof in amount 0.05 to 20.0 % by weight. Again, reaction product is separated after cooling through simple separation and/or rectification into fractions: hydrocarbon gas, gasoline, kerosene, and/or diesel fractions, after which catalyst is regenerated by oxygen-containing gas at 350-600°C and pressure 0.1-6 MPa.

EFFECT: improved flexibility of process and enlarged assortment of raw materials and target products.

12 cl, 3 tbl, 22 ex

FIELD: petrochemical processes.

SUBSTANCE: hydrocarbon feedstock, containing narrow and wide hydrocarbon fractions boiling within a range from boiling point to 205°C and C1-C4-alcohols and/or dimethyl ether, which are blended in a system, to which they are supplied separately (by two pumps) at volume ratio (20.0-90.0):(10-80), respectively, is brought into contact with zeolite-containing catalyst at 380-420°C, pressure 0.2-5.0 MPa, and liquid feedstock volume flow rate 0.5-2.0·h-1, whereupon reaction products are liberated from water produced in the reaction. Above-mentioned zeolite-containing catalyst is comprised of (i) Pentasil-type zeolite with silica ratio (SiO2/Al2O3) 25-100 in amount 65-70% including residual amount of sodium ions equivalent to 0.05-0.1% sodium oxide, (ii) modifiers: zinc oxide (0.5-3.0%), rare-earth element oxides (0.1-3.0%), cobalt oxide (0.05-2.5%) or copper chromite (0.1-0.3%), and (iii) binder: alumina or silica in balancing amount.

EFFECT: increased octane number of gasoline.

2 tbl, 9 ex

FIELD: petrochemical processes.

SUBSTANCE: feedstock is brought into contact with catalyst based on Pentasil family zeolite in at least two zones differing from each other in conditions of conversion of aliphatic hydrocarbons into aromatic hydrocarbons, first in low-temperature conversion zone to covert more active feedstock components to produce aromatic hydrocarbons containing product followed by recovering C5+-hydrocarbons therefrom and, then, contacting the rest of hydrocarbons produced in low-temperature conversion zone with catalyst in high-temperature conversion zone, wherein less active component(s) is converted into aromatic hydrocarbons containing product followed by recovering C5+-hydrocarbons therefrom.

EFFECT: enabled production of aromatic hydrocarbons under optimal conditions from feedstock containing aliphatic C1-C4-hydrocarbons with no necessity of separating the latter.

4 cl, 1 dwg, 1 tbl

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: invention relates to catalysts for isomerization of paraffins and alkylation of unsaturated and aromatic hydrocarbons contained in hydrocarbon stock. Catalyst of invention is characterized by that it lowers content of benzene and unsaturated hydrocarbons in gasoline fractions in above isomerization and alkylation process executed in presence of methanol and catalyst based on high-silica ZSM-5-type zeolite containing: 60.0-80.0% of iron-alumino-silicate with ZSM-5-type structure and silica ratio SiO2/Al2O3 = 20-160 and ratio SiO2/Fe2O3 = 30-550; 0.1-10.0% of modifying component selected from at least one of following metal oxides: copper, zinc, nickel, gallium, lanthanum, cerium, and rhenium; 0.5-5.0% of reinforcing additive: boron oxide, phosphorus oxide, or mixture thereof; the rest being alumina. Preparation of catalyst includes following steps: hydrothermal crystallization of reaction mixture at 120-180°C during 1 to 6 days, said reaction mixture being composed of precursors of silica, alumina, iron oxide, alkali metal oxide, hexamethylenediamine, and water; conversion of thus obtained iron-alumino-silicate into H-iron-alumino-silicate; further impregnation of iron-alumino-silicate with modifying metal compound followed by drying operation for 2 to 12 h at 110°C; mixing of dried material with reinforcing additive, with binder; mechanochemical treatment on vibrating mill for 4 to 72 h; molding catalyst paste; drying it for 0.1 to 24 h at 100-110°C; and calcination at 550-600°C for 0.1 to 24 h. Lowering of content of benzene and unsaturated hydrocarbons in gasoline fractions in presence of above catalyst is achieved during isomerization and alkylation of hydrocarbon feedstock carried out at 300-500°C, volumetric feedstock supply rate 2-4 h-1, weight ratio of hydrocarbon feedstock to methanol 1:(0.1-0.3), and pressure 0.1 to 1.5 MPa. In particular, hydrocarbon feedstock utilized is fraction 35-230°C of hydrostabilized liquid products of pyrolysis.

EFFECT: facilitated reduction of benzene and unsaturated hydrocarbons in gasoline fractions and other hydrocarbon fuel mixtures.

3 cl, 1 tbl, 13 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: hydrocarbon feed is converted in presence of porous catalyst at 250-500°C and pressure not higher than 2.5 MPa, feed uptake being not higher than 10 h-1. Hydrocarbon feed utilized are various-origin hydrocarbon distillates with dry point not higher than 400°C. Catalyst is selected from various aluminosilicate-type zeolites, gallosilicates, galloaluminosilicate, ferrosilicates, ferroaluminosilicates, chromosilicates, and chromoaluminosilicates with different elements incorporated into structure in synthesis stage. Resulting C1-C5-hydrocarbons are separated from gasoline and diesel fuel in separator and passed to second reactor filled with porous catalyst, wherein C1-C5-hydrocarbons are converted into concentrate of aromatic hydrocarbons with summary content of aromatics at least 95 wt %. In other embodiments of invention, products leaving second reactor are separated into gas and high-octane fraction. The latter is combined with straight-run gasoline fraction distilled from initial hydrocarbon feedstock.

EFFECT: increased average production of liquid products.

18 cl, 3 dwg, 9 ex

FIELD: petrochemical processes.

SUBSTANCE: high-octane fuels and propane-butane fraction are obtained via conversion of hydrocarbon feedstock on contact with hot catalyst placed in reactor, into which diluting gas is supplied at elevated pressure. Catalyst is Pentasil-type zeolite with general formula xM2/nO,xAl2O3,ySiO2,zMe2/mO wherein M represents hydrogen and/or metal cation, Me group II or VII metal, n is M cation valence, m is Me metal valence, x, y, z are numbers of moles of Al2O3, SiO2, and Me2/mO, respectively, and y/x and y/z ratios lie within a range of 5 to 1000. Metal oxide Me2/mO is formed during calcination, in presence of oxygen, of Me-containing insoluble compound obtained in zeolite reaction mixture.

EFFECT: increased octane number of gasoline fractions with propane-butane fraction as chief component of gas products, and prolonged inter-regeneration time of catalyst.

11 cl, 4 dwg, 3 tbl, 16 ex

The invention relates to the technology of organic synthesis, namely, catalytic methods of processing of hydrocarbon raw materials to produce products, which can be used either directly as motor fuel or as a component of a fuel or as raw material for separation of aromatic hydrocarbons and a catalyst for the implementation of these methods

FIELD: petrochemical processes.

SUBSTANCE: high-octane fuels and propane-butane fraction are obtained via conversion of hydrocarbon feedstock on contact with hot catalyst placed in reactor, into which diluting gas is supplied at elevated pressure. Catalyst is Pentasil-type zeolite with general formula xM2/nO,xAl2O3,ySiO2,zMe2/mO wherein M represents hydrogen and/or metal cation, Me group II or VII metal, n is M cation valence, m is Me metal valence, x, y, z are numbers of moles of Al2O3, SiO2, and Me2/mO, respectively, and y/x and y/z ratios lie within a range of 5 to 1000. Metal oxide Me2/mO is formed during calcination, in presence of oxygen, of Me-containing insoluble compound obtained in zeolite reaction mixture.

EFFECT: increased octane number of gasoline fractions with propane-butane fraction as chief component of gas products, and prolonged inter-regeneration time of catalyst.

11 cl, 4 dwg, 3 tbl, 16 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: hydrocarbon feed is converted in presence of porous catalyst at 250-500°C and pressure not higher than 2.5 MPa, feed uptake being not higher than 10 h-1. Hydrocarbon feed utilized are various-origin hydrocarbon distillates with dry point not higher than 400°C. Catalyst is selected from various aluminosilicate-type zeolites, gallosilicates, galloaluminosilicate, ferrosilicates, ferroaluminosilicates, chromosilicates, and chromoaluminosilicates with different elements incorporated into structure in synthesis stage. Resulting C1-C5-hydrocarbons are separated from gasoline and diesel fuel in separator and passed to second reactor filled with porous catalyst, wherein C1-C5-hydrocarbons are converted into concentrate of aromatic hydrocarbons with summary content of aromatics at least 95 wt %. In other embodiments of invention, products leaving second reactor are separated into gas and high-octane fraction. The latter is combined with straight-run gasoline fraction distilled from initial hydrocarbon feedstock.

EFFECT: increased average production of liquid products.

18 cl, 3 dwg, 9 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: invention relates to catalysts for isomerization of paraffins and alkylation of unsaturated and aromatic hydrocarbons contained in hydrocarbon stock. Catalyst of invention is characterized by that it lowers content of benzene and unsaturated hydrocarbons in gasoline fractions in above isomerization and alkylation process executed in presence of methanol and catalyst based on high-silica ZSM-5-type zeolite containing: 60.0-80.0% of iron-alumino-silicate with ZSM-5-type structure and silica ratio SiO2/Al2O3 = 20-160 and ratio SiO2/Fe2O3 = 30-550; 0.1-10.0% of modifying component selected from at least one of following metal oxides: copper, zinc, nickel, gallium, lanthanum, cerium, and rhenium; 0.5-5.0% of reinforcing additive: boron oxide, phosphorus oxide, or mixture thereof; the rest being alumina. Preparation of catalyst includes following steps: hydrothermal crystallization of reaction mixture at 120-180°C during 1 to 6 days, said reaction mixture being composed of precursors of silica, alumina, iron oxide, alkali metal oxide, hexamethylenediamine, and water; conversion of thus obtained iron-alumino-silicate into H-iron-alumino-silicate; further impregnation of iron-alumino-silicate with modifying metal compound followed by drying operation for 2 to 12 h at 110°C; mixing of dried material with reinforcing additive, with binder; mechanochemical treatment on vibrating mill for 4 to 72 h; molding catalyst paste; drying it for 0.1 to 24 h at 100-110°C; and calcination at 550-600°C for 0.1 to 24 h. Lowering of content of benzene and unsaturated hydrocarbons in gasoline fractions in presence of above catalyst is achieved during isomerization and alkylation of hydrocarbon feedstock carried out at 300-500°C, volumetric feedstock supply rate 2-4 h-1, weight ratio of hydrocarbon feedstock to methanol 1:(0.1-0.3), and pressure 0.1 to 1.5 MPa. In particular, hydrocarbon feedstock utilized is fraction 35-230°C of hydrostabilized liquid products of pyrolysis.

EFFECT: facilitated reduction of benzene and unsaturated hydrocarbons in gasoline fractions and other hydrocarbon fuel mixtures.

3 cl, 1 tbl, 13 ex

FIELD: petrochemical processes.

SUBSTANCE: feedstock is brought into contact with catalyst based on Pentasil family zeolite in at least two zones differing from each other in conditions of conversion of aliphatic hydrocarbons into aromatic hydrocarbons, first in low-temperature conversion zone to covert more active feedstock components to produce aromatic hydrocarbons containing product followed by recovering C5+-hydrocarbons therefrom and, then, contacting the rest of hydrocarbons produced in low-temperature conversion zone with catalyst in high-temperature conversion zone, wherein less active component(s) is converted into aromatic hydrocarbons containing product followed by recovering C5+-hydrocarbons therefrom.

EFFECT: enabled production of aromatic hydrocarbons under optimal conditions from feedstock containing aliphatic C1-C4-hydrocarbons with no necessity of separating the latter.

4 cl, 1 dwg, 1 tbl

FIELD: petrochemical processes.

SUBSTANCE: hydrocarbon feedstock, containing narrow and wide hydrocarbon fractions boiling within a range from boiling point to 205°C and C1-C4-alcohols and/or dimethyl ether, which are blended in a system, to which they are supplied separately (by two pumps) at volume ratio (20.0-90.0):(10-80), respectively, is brought into contact with zeolite-containing catalyst at 380-420°C, pressure 0.2-5.0 MPa, and liquid feedstock volume flow rate 0.5-2.0·h-1, whereupon reaction products are liberated from water produced in the reaction. Above-mentioned zeolite-containing catalyst is comprised of (i) Pentasil-type zeolite with silica ratio (SiO2/Al2O3) 25-100 in amount 65-70% including residual amount of sodium ions equivalent to 0.05-0.1% sodium oxide, (ii) modifiers: zinc oxide (0.5-3.0%), rare-earth element oxides (0.1-3.0%), cobalt oxide (0.05-2.5%) or copper chromite (0.1-0.3%), and (iii) binder: alumina or silica in balancing amount.

EFFECT: increased octane number of gasoline.

2 tbl, 9 ex

FIELD: petrochemical processes.

SUBSTANCE: group of inventions relates to processing of hydrocarbon feedstock having dry point from 140 to 400°C and is intended for production of fuel fractions (gasoline, kerosene, and/or diesel) on solid catalysts. In first embodiment of invention, processing involves bringing feedstock into contact with regenerable catalyst at 250-500°C, pressure 0.1-4 MPa, and feedstock weight supply rate up to 10 h-1, said catalyst containing (i) crystalline silicate or ZSM-5 or ZSM-14-type zeolite having general empiric formula: (0.02-0.35)Na2O-E2O3-(27-300)SiO2-kH2O), where E represents at least one element from the series: Al, Ga, B, and Fe and k is coefficient corresponding to water capacity; or (ii) silicate or identically composed zeolite and at least one group I-VIII element and/or compound thereof in amount 0.001 to 10.0 % by weight. Reaction product is separated after cooling through simple separation and/or rectification into fractions: hydrocarbon gas, gasoline, kerosene, and/or diesel fractions, after which catalyst is regenerated by oxygen-containing gas at 350-600°C and pressure 0.1-4 MPa. Hydrocarbon feedstock utilized comprises (i) long hydrocarbon fraction boiling away up to 400°C and composed, in particular, of isoparaffins and naphtenes in summary amount 54-58.1%, aromatic hydrocarbons in amount 8.4-12.7%, and n-paraffins in balancing amount; or (ii) long hydrocarbon fraction boiling away up to 400°C and composed, in particular, of following fractions, °C: 43-195, 151-267, 130-364, 168-345, 26-264, 144-272. In second embodiment, feedstock boiling away up to 400°C is processed in presence of hydrogen at H2/hydrocarbons molar ratio between 0.1 and 10 by bringing feedstock into contact with regenerable catalyst at 250-500°C, elevated pressure, and feedstock weight supply rate up to 10 h-1, said catalyst containing zeolite having structure ZSM-12, and/or beta, and/or omega, and/or zeolite L. and/or mordenite, and/or crystalline elemento-aluminophosphate and at least one group I-VIII element and/or compound thereof in amount 0.05 to 20.0 % by weight. Again, reaction product is separated after cooling through simple separation and/or rectification into fractions: hydrocarbon gas, gasoline, kerosene, and/or diesel fractions, after which catalyst is regenerated by oxygen-containing gas at 350-600°C and pressure 0.1-6 MPa.

EFFECT: improved flexibility of process and enlarged assortment of raw materials and target products.

12 cl, 3 tbl, 22 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention provides isodewaxing catalyst for petroleum fractions containing supported platinum and modifiers wherein supporting carrier is fine powdered high-purity alumina mixed with zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40 at following proportions of components, wt %: platinum 0.15-0.60, alumina 58.61-89.43, zeolite 5-40, tungsten oxide (modifier) 1-4, and indium oxide (modifier) 0.24-0.97. Preparation of catalyst comprises preparing carrier using method of competitive impregnation from common solution of platinum-hydrochloric, acetic, and hydrochloric acids followed by drying and calcinations, wherein carrier is prepared by gelation of fine powdered high-purity alumina with the aid of 3-15% nitric acid solution followed by consecutive addition of silicotungstenic acid solution and indium chloride solution, and then zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40.

EFFECT: increased yield of isoparaffin hydrocarbons.

7 cl, 2 tbl, 7 ex

FIELD: CHEMISTRY.

SUBSTANCE: zeolite catalyst for process of conversion of straight-run gasoline to high-octane number component is described. The said catalyst contains high-silica zeolite with SiO2/Al2O3=60 and residual content of Na2О of 0.02 wt.% maximum, metal-modified, Pt, Ni, Zn or Fe metals being in nanopowder form. Content of the said metals in the catalyst is 1.5 wt.% maximum. Method to manufacture zeolite catalyst for conversion of straight-run gasoline to high-octane number component is described. The said method implies metal modification of zeolite, Pt, Ni, Zn or Fe metals being added to zeolite as nanopowders, produced by electric explosion of metal wire in argon, by dry pebble mixing in air at room temperature. Method to convert straight-run gasoline using the said catalyst is also described.

EFFECT: increase in catalyst activity and gasoline octane number, accompanied by increase in yield.

4 cl, 3 tbl, 4 ex

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 refers to production method of high-octane gasoline fractions and/or aromatic hydrocarbons C6-C10 as follows, hydrocarbon materials is heated, evaporated and overheated to process temperature, thereafter providing its contact at temperature 320-480°C and excess pressure with periodically recyclable catalyst containing zeolite of composition ZSM-5 or ZSM-11. Then it is cooled. Contact products are partially condensed, separated into gaseous and liquid fractions by separation. Liquid products of separation are supplied as power primarily to the first distillation column for separation of hydrocarbon gases and liquid stable fraction. The latter is supplied to the second distillation column for separation of high-octane gasoline fraction, or aromatic hydrocarbon fraction, and heavy charge fraction. Gaseous fraction resulted from separation of contact products is supplied to the first distillation column, specifically to intermediate section between infeed and external reflux inlet. External reflux is liquid distillate of the first distillation column.

EFFECT: reduction of power inputs, i.e. quantities of heat and cooling agent, required for reaction products separation.

5 cl, 2 ex

Up!