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USEFUL ADDITIVES FOR PETROL AND OTHER MOTOR FUELS
INVENTION
Patent of the Russian Federation RU2216569

METHOD OF OBTAINING MOTOR FUELS (OPTIONS)

METHOD OF OBTAINING MOTOR FUELS (OPTIONS)

The name of the inventor: Klimov OV; Aksenov DG; Kikhtyanin OV; Kodenev EG; Echevsky G.V.
The name of the patent holder: GKBoreskov of the SB RAS
Address for correspondence: 630090, Novosibirsk, Acad. Lavrentyeva, 5, Institute of Catalysis named after. GK Boreskov, Patent Department, T.D. Yudina
Date of commencement of the patent: 2002.10.30

Use: petrochemistry. Essence: processing of hydrocarbon raw materials into gasoline with the boiling point not higher than 195 o C and octane number not lower than 83 by the motor method, as well as in diesel fuel with cetane number not lower than 50 and pour point not higher than -35 o C, consisting in transformation Hydrocarbon feedstock in the presence of a porous catalyst at a temperature of 250-500 ° C, a pressure of not more than 2.5 MPa, a mass flow of a hydrocarbon mixture of not more than 10 h -1 , while hydrocarbon distillates of different origin with a boiling point not exceeding 400 O C. The gases formed during the reaction are separated from the liquid products and subjected to processing with the formation of additional amounts of the gasoline fraction. The technical result: creation of an improved method for obtaining motor fuels.

DESCRIPTION OF THE INVENTION

The invention relates to the production of motor fuels, namely to catalytic processes for the production of high-octane gasoline and high-density diesel fuel with a low freezing point from various hydrocarbon feedstocks.

There are a number of ways to obtain motor fuels from a hydrocarbon feed in the presence of catalysts. A method for obtaining motor fuels from fractions of gas condensate on zeolite catalysts is known [Agabalyan LG. Catalytic processing of straight-run fractions of gas condensate into high-octane fuels. - Chemistry and Technology of Fuels and Oils, 1988, N 5, p.6]. According to this method, high-octane gasolines are produced by the "Zeoforming" process from straight-run gasoline fractions separated from gas condensates along with gaseous, straight-run diesel and residual fractions. The "Zeoforming" process is carried out as follows: the straight-run gasoline fraction is separated with the separation of fractions of NK-58 ° C. and> 58 ° C., the second fraction is contacted at elevated temperatures (up to 460 ° C.) and overpressure (up to 5 MPa) with the zeolite-containing catalyst . The reaction products are fractionated with evolution of hydrocarbon gases, a residual fraction> 195 ° C. and a high-octane fraction <195 C, which is compounded with a fraction of NK-58 ° C to obtain the target gasoline. The main drawbacks of this method are relatively low yields and octane numbers of gasoline produced, high pour point of diesel fuel and (in some cases) a low cetane number.

A method for obtaining high-octane gasoline and diesel fuel from fractions of gas condensate is known [Pat. RF 2008323, C 10 G 51/04, 28.02.94]. According to this method, the stable gas condensate is fractionated with the following straight-run fractions: gasoline, boiling up to 140-200 ° C., diesel boiling within 140-340 ° C., and residual boiling above 340 ° C. The residual fraction or its mixture with gaseous The products of the reaction are pyrolyzed at a temperature of 600-900 ° C. Pyrolysis products are fractionated with evolution of gaseous and liquid fractions. The pyrogas is mixed with a straight-run gasoline fraction and contacted with a zeolite-containing catalyst. The contacting products are fractionated with the evolution of hydrocarbon gases and a gasoline fraction which is compounded with the pyro-condensate and subjected to rectification to isolate the target gasoline fr. НК-195 o С and residual fraction> 185 o С. In this method the output of the target gasoline fraction is 46.8% in terms of stable gas condensate or 82.4% per straight-run gasoline fraction. The resulting diesel fuel is a typical straight-run fuel - it has a cetane number of not more than 45 and a pour point of at least -10 ° C, while according to the World Fuel Charter, a cetane number not lower than 55 corresponds to high-quality diesel fuel [Vipper AB. , Ermolaev MV World Fuel Charter. - Oil refining and petrochemistry, 1999, N 6, pp. 50-55].

The main disadvantages of this method of obtaining motor fuels are the complexity of the technology for obtaining high-octane gasolines due to multiple fractionation of the hydrocarbon mixture, relatively low yields of target gasoline fractions based on the converted feed, and a low cetane number and a high freezing point of the diesel fuel produced.

The most similar in its technical essence and achieved effect is the method of processing petroleum distillates [Pat. RF N 2181750, C 10 G 35/095, 19.04.2001]. According to this method, an oil distillate with a boiling point of not more than 400 ° C., containing sulfur compounds in amounts of not more than 10% by weight, based on elemental sulfur, at a temperature of 250-500 ° C., a pressure of not more than 2 MPa, 10 h -1 are contacted with a porous catalyst, which uses a zeolite of an aluminosilicate composition with a SiO 2 / Al 2 O 3 molar ratio of not more than 450, selected from the ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM -48, BETA. According to this method, the yields of the gasoline fraction lie in the range of 52.4-66.7% by weight, based on the initial distillate, the octane number of gasoline obtained, determined by the motor method is 81.3-88.3. The diesel fuel obtained with an outlet of 26-36% by weight has a cetane number of 45-50 at a pour point of at least -35 ° C. In addition to these products, a gas containing a C 3 -C 4 fraction in an amount of 10-15% by weight is produced in calculation To the original distillate, and a certain amount of hydrogen, hydrogen sulfide and dry gas (C 1 -C 2 ).

The main drawback of the known method is the reduction in the yield of the gasoline fraction in terms of the converted feedstock due to the conversion of some of the liquid feedstock into gaseous products under normal conditions.

The proposed invention solves the problem of creating an improved method for producing motor fuels characterized by an increased yield of high-octane gasoline with at least the quality of the products obtained being at least as good as the prototype - an octane number of gasoline of at least 84 by the motor method, for diesel fuel, the cetane number is not less than 50 And the pour point is not higher than -35 ° C.

The task is solved by a method for processing hydrocarbon feedstock into gasoline with a boiling point not higher than 195 ° C. and octane number not lower than 83 by the motor method, but also in diesel fuel with a cetane number not lower than 50 and a pour point not higher than -35 ° C., Conversion of the hydrocarbon feedstock in the presence of a porous catalyst at a temperature of 250-500 ° C, a pressure of not more than 2.5 MPa, mass flow rates of a hydrocarbon mixture of not more than 10 h -1 , while hydrocarbon distillates of different origin with a boiling point not higher than 400.degree . C., and zeolite of an aluminosilicate composition with a SiO.sub.2 / Al.sub.2 O.sub.3 molar ratio of not more than 450 selected from the group ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA Or gallosilicate, galloaluminosilicate, iron silicate, iron-aluminosilicate, chromium silicate, chromalumosilicate with the structure ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or alumophosphate with the structure of the type Alpo-5, Alpo-11, A1PO-31, A1PO-41, A1PO-36, A1PO-37, A1PO-40 with an element selected from the synthesis stage: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium or any of them mixture.

The main distinguishing feature of the proposed method is that the gases formed during the reaction are separated from the liquid products and subjected to processing with the formation of additional amounts of the gasoline fraction.

The first variant of gas processing consists in the fact that at the outlet of the reactor the products are divided in a separator into a mixture of motor fuels and a gas phase, which is further divided into hydrogen-containing dry gas, hydrogen sulfide and a C3-C4 fraction, followed by mixing of the latter with a hydrocarbon feed stream At the inlet to the reactor, hydrogen sulphide and hydrogen are extracted from the gas, and the entire hydrocarbon component of C 1 -C 4 is returned to the inlet of the reactor, or the gas is returned to the reactor inlet without fractionation and separation of any constituents, however, part of the gas is withdrawn from the reaction loop , So that the weight flow of gas through the reactor lies in the interval 0.1-5 h -1 .

The second variant of the solution of the problem differs from the first in that, after separation from the liquid reaction products, the gas is sent to a second reactor, containing as catalyst a zeolite of an aluminosilicate composition with a SiO2 / Al2O3 molar ratio of not more than 450, selected from the ZSM-5 series, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or gallosilicate, galloaluminosilicate, iron silicate, iron aluminosilicate, chromium silicate, chromaluminosilicate with the structure of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM- 48, BETA, or alumophosphate with the structure of the type selected from the series: magnesium, Alpo-5, Alpo-11, Alpo-31, Alpo-41, Alpo-36, Alpo-37, Alpo-40, , Zinc, gallium, manganese, iron, silicon, cobalt, cadmium, or any mixture thereof. The process of gas transformation is carried out at a temperature of 300-600 ° C, at a pressure of up to 2.5 MPa and a gas flow rate of 0.1-5 h -1 . The second reactor is fed either all of the gas from the first reactor without separating it into separate components, or the hydrocarbon component of C 1 -C 4 is separated from the gas, which is sent to the second reactor, or only the C 3 -C 4 fraction is separated from the gas, which is fed to Second reactor. Further, the liquid products formed in the second reactor are mixed with the gasoline fraction from the first reactor.

The catalyst used for each process variant, as well as in the second reactor in the second process variant, may contain a compound of at least one of the series metals: zinc, gallium, nickel, cobalt, molybdenum, tungsten, rhenium, rare earths, platinum metals Group, in an amount of not more than 10% by weight. The catalyst for each variant of the process is prepared by adding the additive by impregnation and / or by ion exchange at a temperature of more than 20 ° C., or by adding an additive from the gas phase, or by adding the additive by mechanical mixing with the starting material, followed by drying and calcination.

The technical effect of the proposed method is that when the C 2 -C 4 gases are converted, an additional amount of a high-octane gasoline component is formed, which leads to an increase in the yield of the gasoline fraction, based on the converted liquid hydrocarbon feed, by 10% or more, with the octane number of the produced gasoline In comparison with the prototype, it increases by 1-2 points.

The method is carried out as follows

As a starting material for the preparation of the catalyst, one of the materials selected from the series of either zeolites ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA with a SiO2 / Al2O molar ratio 3 not more than 450, gallosilicates and galloaluminosilicates, iron silicates, iron aluminosilicates, chromium silicates, chromaluminosilicates with the structure of ZSM-5 and / or ZSM-11, ZSM-48, BETA, or aluminophosphates with structures of the type ALPO-5, -1, -31, - 41, -36, -37, -40, with elements selected from the series at the synthesis stage: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium, or any mixture thereof.

Further, the starting material, if necessary, is modified by introducing into its composition compounds of at least one of the metals of the series: zinc, gallium, nickel, cobalt, molybdenum, tungsten, rhenium, rare earth elements, platinum group metals in an amount of not more than 10% by weight.

Modification of the zeolite is carried out by impregnation, activated impregnation in an autoclave, application from a gas phase, ion exchange, mechanical mixing of components. After introduction of the modifying additive, the catalyst is dried and calcined at temperatures up to 600 ° C.

The resulting catalyst is placed in a flow reactor, purged either with nitrogen or with an inert gas or a mixture thereof at temperatures up to 600 ° C, after which liquid hydrocarbon feed is supplied at mass flow rates up to 10 h -1 , temperatures 250-500 ° C, 2.5 MPa.

After leaving the reactor, the products, after cooling in the refrigerator, are fed to a separator where the gas and liquid components are separated. Further, liquid products are divided by distillation into gasoline and diesel fuel.

In a first variant of the process, a portion of the gas fraction is returned to the reactor inlet where it is mixed with the liquid hydrocarbon feed, another portion of the gas is withdrawn from the plant and used as fuel. The ratio of gas parts is selected in such a way that the weight flow of gas through the reactor lies in the interval 0.1-5 h -1 . In the event that the feed hydrocarbon feed contains a large amount of sulfur, the gases leaving the separator are subjected to hydrogen sulfide purification by a standard procedure, for example using monoethanolamine, and then returned to the reactor inlet. If necessary, only the C 3 -C 4 fraction is returned to the reactor inlet, which is previously separated from the gas by one of the known methods, for example by low-temperature separation.

The choice of this or that gas recycling case is determined by the process economics applied to a particular type of feedstock and the required quantity and quality of the gasoline produced.

According to a second variant of the method, the gas after the separator is sent to a second reactor filled with a catalyst of the ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA zeolite zeolite with a SiO 2 / Al 2 O 3 molar ratio of at most 450, gallosilicates and galloaluminosilicates, iron silicates, iron aluminosilicates, chromium silicates, chromaluminosilicates with the structure of ZSM-5 and / or ZSM-11, ZSM-48, BETA, or alumophosphates with structures of the type ALPO-5, -11, -31, -41, - 36, -37, -40 with elements introduced into the structure at the stage of synthesis: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium or any mixture thereof.

The catalyst can additionally contain a compound of at least one of the metals of the series: zinc, gallium, nickel, cobalt, molybdenum, tungsten, rhenium, rare earth elements, platinum group metals, in an amount of not more than 10% by weight. The addition to the catalyst is impregnated and / or ion exchanged at a temperature of more than 20 ° C. or is applied from the gas phase, or is introduced by mechanical mixing with the starting material, followed by drying and calcination.

The catalyst loaded into the second reactor is pre-purged either with nitrogen, or with hydrogen, or with methane, or with dry gas or with an inert gas, or with a mixture at temperatures up to 600 ° C, then at temperatures of 300-600 ° C and a pressure of not more than 2.5 MPa starts supplying either the whole mixture of gases leaving the separator or the gas that has been purified from hydrogen sulfide in the same way as option 1 or the C 3 -C 4 fraction separated from the gas mixture in the same way as option 1, with the weight flow of gas through the second reactor lying in the interval 0.1-5 h- 1 .

At the outlet of the second reactor, the products enter the separator, where they are separated into liquid and gas fractions. Gas, if necessary, is used to heat the reactors, and the liquid fraction is mixed with gasoline obtained in the first reactor.

The following examples describe in detail the present invention and illustrate its implementation.

Example 1 . From the ZSM-5 zeolite powder with the molar ratio SiO 2 / Al 2 O 3 = 60, a fraction of 0.2-0.8 mm is prepared. 5 g of the obtained catalyst is placed in a flow reactor, purged with nitrogen (5 l / h) at a temperature of 500 ° C for 2 hours, then the temperature is lowered to 350 ° C and the nitrogen supply is stopped. Further, at this temperature and atmospheric pressure, starting feed of the distillate is started at-250 ° C with a mass feed rate of 1.5 h -1 . At the outlet from the reactor, the products are cooled to room temperature and separated in a separator into a liquid and a gas phase, the liquid phase is collected for 8 hours, then dispersed to gasoline NK-195 ° C and diesel fuel 195-360 ° C. The gas is sent to a second separator , Cooled to -50 ° C. where a C 3+ fraction is recovered from it, which is then returned to the reactor inlet by a pump. In this mode of operation, the average yield of the gasoline fraction was 72.4% by weight, the octane number by MM 89.5, the yield of diesel fuel 12.8% by weight, cetane number 52, the pour point -39 ° C.

Example 2 . 30 g of BETA zeolite powder with a molar ratio of SiO 2 / Al 2 O 3 = 26 is filled with 1 liter of an aqueous solution containing 15 g of Ga (NO 3 ) 3× 8H 2 O. The resulting suspension is boiled with stirring and reflux for 4 hours, after which The powder is separated on a filter, washed repeatedly with distilled water and dried. The resulting sample was dried at 100 ° C., calcined at 550 ° C., after which a fraction of 0.2-0.8 mm was prepared. The catalyst contains 0.7% by weight of gallium.

5 g of the obtained catalyst is placed in a flow reactor, purged with nitrogen (5 l / h) at a temperature of 500 ° C for 2 hours, then the temperature is lowered to 350 ° C and the nitrogen supply is stopped. Further, at this temperature and at atmospheric pressure, the starting distillate HK-300 ° C begins to feed at a mass feed rate of 2.4 h -1 .

The product separation and the gas circulation are then carried out in the same manner as in Example 1. The average yield of the gasoline fraction was 74.9% by weight, the octane rating of MM 88.5, the yield of diesel fuel 11.3% by weight, the cetane number 54, the pour point -37 ° FROM.

Example 3 . A mechanical mixture of 30 g of iron silicate with the structure of ZSM-11 and 3 g of WO 3 is prepared. The resulting sample was calcined at 550 ° C. for 4 hours, after which a fraction of 0.2-0.8 mm was prepared.

5 g of the obtained catalyst is placed in a flow reactor, purged with nitrogen (5 l / h) at a temperature of 500 ° C for 2 hours, then the temperature is lowered to 400 ° C and the nitrogen supply is stopped. Further, at this temperature and atmospheric pressure, starting feed of the distillate is started at-250 ° C (sulfur content 0.5% by weight) with a mass feed rate of 2.1 h -1 . The product separation and the gas circulation are then carried out in the same manner as in Example 1, except that the temperature in the low-temperature separator is -90 ° C. and a mixture of C 1 -C 4 and hydrogen sulfide gas is supplied to the circulation. In this case, the yield of the gasoline fraction is 73.1% by weight, the octane number is MM 86.2, the yield of diesel fuel is 12.2% by weight, the cetane number is 51, the pour point is -39 ° C.

Example 4 . 20 g of ZSM-48 aluminosilicate are purged with nitrogen containing molybdenum acetylacetonate at a temperature of 250 ° C. After the amount of molybdenum passed through the sample corresponds to the molybdenum content in the sample of 5%, the nitrogen supply is stopped, the sample is blown with air at a temperature of 560 ° C C for 2 hours. Then a 0.2-0.8 mm fraction is prepared.

5 g of the obtained catalyst is placed in a flow reactor, purged with nitrogen (5 l / h) at a temperature of 500 ° C for 2 hours, then the temperature is lowered to 350 ° C and the nitrogen supply is stopped. Further, at this temperature and a pressure of 2.5 MPa, starting feedstock distillate of NK-300 ° C (sulfur content 1% by weight) is started at a mass feed rate of 1.4 h -1 . The product separation and gas circulation are then carried out in the same manner as in Example 3. In this case, the yield of the gasoline fraction is 69.5% by weight, the octane rating is MM 87.5, the diesel yield is 16.6% by weight, the cetane number is 54, the pour point is -36 ° C.

Example 5 . 5 g of the catalyst of example 4 are placed in a flow reactor, purged with nitrogen (5 l / h) at 500 ° C for 2 hours, then the temperature is lowered to 350 ° C and the nitrogen supply is stopped. Further, at this temperature and at atmospheric pressure, the initial distillate is started to flow with HK-300 ° C (sulfur content 1% by weight) with a mass feed rate of 2.8 -1 . The product separation and gas circulation are then carried out in the same manner as in Example 3, with the difference that, after the first separator, the gases are purified from hydrogen sulfide by contact with monoethanolamine (the content of hydrogen sulfide in the purified gas is not more than 0.0003% by volume). In this case, the yield of the gasoline fraction is 73.7% by weight, the octane number by MM 86.9, the yield of diesel fuel 14.8% by weight, the cetane number 55, the pour point is -35 ° C.

Example 6 . 30 g of aluminophosphate with the AlBO-31 structure containing 1.4 wt% Si introduced into the structure during the hydrothermal synthesis is impregnated with a solution of nickel nitrate at a rate of 1.5 wt% Ni in the final catalyst. The catalyst was calcined for 2 hours at a temperature of 600 ° C., after which a fraction of 0.2-0.8 mm was prepared.

10 g of the obtained catalyst is placed in a flow reactor, purged with nitrogen (5 l / h) at a temperature of 500 ° C for 2 hours, then the temperature is lowered to 400 ° C and the nitrogen supply is stopped. Further, at this temperature and a pressure of 0.5 MPa, starting feed of an initial distillate of NK-300 ° C containing 1.0 wt.% Sulfur is started at a mass feed rate of 1.4 h -1 . The product separation and the gas circulation are then carried out in the same way as in Example 1, except that after the first separator, the gases are purified from hydrogen sulfide by contact with monoethanolamine (the content of hydrogen sulfide in the fraction of C 3+ recovered to the reactor inlet is not more than 0.0003% by volume). In this case, the yield of the gasoline fraction is 68.7% by weight, the octane number by MM 88.1, the yield of diesel fuel 13.7% by weight, the cetane number 56, the pour point is -36 ° C.

Example 7 . A fraction of 0.2-0.8 mm is prepared from a powder of galliumaluminosilicate with a ZSM-5 structure. 7 g of the obtained catalyst is placed in a flow reactor, purged with nitrogen (5 l / h) at a temperature of 500 ° C for 2 hours, then the temperature is lowered to 350 ° C and the nitrogen supply is stopped. Further, at this temperature and pressure of 2 MPa, starting feed of an initial distillate HK-400 ° C containing 3.5 wt. % Sulfur with a mass feed rate of 1.3 h -1 .

At the outlet of the reactor, the products are cooled to room temperature and separated in a separator into a liquid and a gas phase, the liquid phase is collected and accelerated similarly to Example 1. The gas is contacted with monoethanolamine to remove hydrogen sulphide and sent to a second separator cooled to -50 ° C, It is separated into a C 3+ fraction which is then fed to the inlet of a second reactor which is filled with a zeolite type ZSM-5 catalyst prepared and activated similarly to Example 1. The temperature in the second reactor is 350 ° C., atmospheric pressure, the catalyst charge corresponds to the weight flow rate of the gas Mixture of 3 h -1 . At the outlet of the second reactor, liquid products are separated in a separator and mixed with the gasoline fraction obtained in the first reactor.

In this mode of operation, the total yield of the gasoline fraction is 68.1% by weight. %, Octane number according to MM 86.0, diesel fuel yield 23.5% by weight, cetane number 54, pour point is -37 ° C.

Example 8 . 5 g of the catalyst of Example 2 (based on GaET-promoted BETA zeolite) were placed in a flow reactor, purged with nitrogen (5 L / h) at a temperature of 500 ° C for 2 hours, then the temperature was lowered to 350 ° C and the nitrogen supply . Further, at this temperature and a pressure of 1 MPa, feed of an initial distillate HK-250 ° C begins at a feed rate of 2.4 h -1 . At the outlet from the reactor, the products are cooled to room temperature and separated in a separator into liquid and gas phases, the liquid phase is collected and accelerated similarly to Example 1. The gas without any purification and separation is sent to a second reactor which is filled with the same catalyst as the first prepared And activated as in Example 2. The temperature in the second reactor is 600 ° C, the pressure is 2.5 MPa, the loading of the catalyst corresponds to a weight flow rate of the gas mixture of 5 h -1 . At the outlet of the second reactor, liquid products are separated in a separator and mixed with the gasoline fraction obtained in the first reactor. In this mode of operation, the total yield of the gasoline fraction is 75.0% by weight. %, Octane number according to MM 90.0, diesel fuel yield 12.1% by weight, cetane number 50, pour point is -38 ° C.

Example 9 . 10 g of the catalyst of Example 6 (alumophosphate with the structure A1PO-31 containing 1.4 wt% Si and 1.5 wt% Ni) are placed in a flow reactor, purged with nitrogen (5 l / h) at a temperature of 500 ° C. in For 2 hours, after which the temperature is lowered to 375 ° C and the nitrogen supply is stopped. Further, at this temperature and a pressure of 1 MPa, feed of an initial distillate HK-350 ° C containing 3.75 wt. % Sulfur, with a mass feed rate of 2.7 h -1 . The products are then separated and accelerated in the same manner as in Example 1, the gases are contacted with monoethanolamine and sent to a second reactor filled with a catalyst prepared from ZSM-5 zeolite powder with a SiO 2 / Al 2 O 3 molar ratio of 60 to which 1, 5% by weight of Zn, the catalyst is preheated in a nitrogen stream at 550 ° C. The temperature in the second reactor is 550 ° C, the pressure is 1.0 MPa, and the gas weight is 2.5 h -1 . At the outlet of the second reactor, liquid products are separated in a separator and mixed with the gasoline fraction obtained in the first reactor. In this mode of operation, the total yield of the gasoline fraction is 74.3% by weight, the octane number by MM 88.3, ​​the yield of diesel fuel is 19.1% by weight, the cetane number is 52, the pour point is -37 ° C.

Example 10 5 g of the catalyst of Example 1 are placed in a flow reactor, purged with nitrogen (5 L / h) at 500 ° C for 2 hours, after which the nitrogen supply is stopped. Further, at this temperature and a pressure of 2.5 MPa, feed of an initial distillate HK-250 ° C containing 0.5% by weight of sulfur begins at a mass flow rate of 10 h -1 . At the outlet of the reactor, the products are cooled to room temperature and separated in a separator into a liquid and a gas phase, the liquid phase is collected and accelerated similarly to Example 1. The gas is contacted with monoethanolamine and passed through a second separator (-120 ° C.) where the fraction C 1- C 4 , which is sent to a second reactor filled with a catalyst prepared in the same manner as in Example 6, except that the Alpo-31 alumophosphate powder is impregnated with an aqueous solution of ammonium perrhenate NH 4 ReO 4 at a rate of 10 wt. % Rhenium in the catalyst, followed by drying and calcination at 600 ° C. The weight flow rate of the gas through the second reactor is 1 h -1 , the temperature is 500 ° C, the pressure is atmospheric. At the outlet of the second reactor, liquid products are separated in a separator and mixed with the gasoline fraction obtained in the first reactor. In this mode of operation, the total yield of the gasoline fraction is 71.2 wt. %, Octane number by MM 86.7, diesel fuel yield 12.1% by weight, cetane number 57, pour point is -35 ° C.

Example 11 . 5 g of the catalyst of Example 1 were placed in a flow reactor, purged with nitrogen (5 L / h) at 500 ° C for 2 hours, then lowered to 350 ° C, nitrogen supply stopped. Further, at this temperature and at atmospheric pressure, starting feed of an initial distillate HK-400 ° C containing 3.5 wt. % Sulfur, with a mass flow rate of 1 h -1 . At the outlet of the reactor, the products are cooled to room temperature and separated in a separator into liquid and gas phases, the liquid phase is collected and accelerated similarly to Example 1. The gas is contacted with monoethanolamine and passed through a second reactor in which chromosilicate is pre-treated at 250 ° C. with nitrogen , Saturated zinc acetylacetonate vapors at a rate of 3% by weight zinc in the catalyst and activated for 2 hours in a stream of air at 550 ° C. and 2 hours in a nitrogen stream at the same temperature. The temperature in the reactor is 500 ° C, the pressure is 0.5 MPa, the gas weight is 1.5 h -1 . At the outlet of the reactor in the separator, a fraction of NK-195 ° C is separated, which is mixed with the gasoline fraction from the first reactor. The total yield of the gasoline fraction was 68.0% by weight, the octane number by MM 87.8, the yield of diesel fuel 25.5% by weight, the cetane number 54, the pour point is -36 ° C.

The advantage of this method over the known method is that the conversion of the hydrocarbon gas into an additional amount of the gasoline component allows the yield of the gasoline fraction to be increased to 68-75% by weight, based on the feed, with the octane number of gasoline reaching 85-90 by the motor method , And diesel fuel has a cetane number not lower than 50 and the pour point is not higher than -35 o C.

CLAIM

1. A method for producing motor fuel, including gasoline with an octane number not lower than 85 by the motor method and diesel fuel with a cetane number not lower than 50 and a pour point of not higher than -35 ° C., consisting in the conversion of hydrocarbon distillates of various origin to the boiling point Not higher than 400 ° C., at a temperature of 250-500 ° C., a pressure of not more than 2.5 MPa, a mass flow rate of a hydrocarbon mixture of not more than 10 h -1 , while a zeolite of an aluminosilicate composition with a SiO 2 / Al 2 molar ratio O 3 not more than 450, selected from the ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or gallosilicate, galloaluminosilicate, iron silicate, iron aluminosilicate, chromium silicate, chromalumosilicate with ZSM-5 structure, ZSM -11, ZSM-35, ZSM-38, ZSM-48, BETA, or alumophosphate with the structure of the type Alpo-5, Alpo-11, Alpo-31, Alpo-41, Alpo-36, Alpo-37, Alpo-40 s A gas selected from the group consisting of magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium, or any mixture thereof, characterized in that the gases formed during the reaction are separated from the liquid products and returned to the inlet of the reactor , Where it is mixed with the starting liquid hydrocarbon feedstock, i.e., recycle the generated gases or parts thereof through a reactor.

2. A process according to claim 1, characterized in that the catalyst comprises a compound of at least one of the series metals: zinc, gallium, nickel, cobalt, molybdenum, tungsten, rhenium, rare earth elements, platinum group metals in an amount of not more than 10 Gt; %.

3. The method of claim 1. 1 and 2, characterized in that the catalyst is prepared by adding the additive by impregnation and / or by ion exchange at a temperature of more than 20 ° C, or by applying an additive from the gas phase, or by adding the additive by mechanically mixing with the starting material, followed by drying and calcination Obtained catalyst.

4. The method of claim 1. 1-3, characterized in that at the outlet of the reactor the products are divided in a separator into a mixture of motor fuels and a gas phase which is further divided into hydrogen-containing dry gas, hydrogen sulfide and a C3-C4 fraction, followed by mixing of the latter with a hydrocarbon feed stream Raw materials at the reactor inlet, or hydrogen sulfide and hydrogen are extracted from the gas, and the entire hydrocarbon component of C 1 -C 4 is recycled to the reactor inlet.

5. A method for producing motor fuel, including gasoline with an octane number not lower than 85 by the motor method and diesel fuel with a cetane number not lower than 50 and a pour point not higher than -35 ° C, consisting in the conversion of hydrocarbon distillates of various origin to the boiling point Not higher than 400 ° C. of the feedstock, at a temperature of 250-500 ° C., a pressure of not more than 2.5 MPa, mass flow rates of the hydrocarbon mixture not more than 10 h -1 , while the catalyst is a zeolite of an aluminosilicate composition with a molar ratio of SiO 2 / Al 2 O 3 not more than 450, selected from the group ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or gallosilicate, galloaluminosilicate, iron silicate, iron-aluminosilicate, chromium silicate, chromalumosilicate with ZSM-5 structure , ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA or alumophosphate with the structure of the type Alpo-5, Alpo-11, Alpo-31, Alpo-41, Alpo-36, Alpo-37, Alpo- 40 with the element selected from the synthesis stage: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium, characterized in that the gases formed during the reaction are separated from the liquid products and sent to a second reactor filled with Porous catalyst, the liquid fraction leaving the second reactor is mixed with gasoline obtained in the first reactor.

6. A process according to claim 5, characterized in that the catalyst used in the second reactor is a ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA zeolite material with a molar ratio SiO 2 / Al 2 O 3 not more than 450, gallosilicates and galloaluminosilicates, iron silicates, iron aluminosilicates, chromium silicates, chromaluminosilicates with the structure of ZSM-5 and / or ZSM-11, ZSM-48, BETA, or aluminophosphates with structures of the type ALPO-5, - 11, -31, -41, -36, -37, -40, with an element chosen in the structure at the synthesis stage: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium or any mixture thereof.

7. The method of claim 1. 5 and 6, characterized in that the catalyst contained in the second reactor contains a compound of at least one of the metals of the series: zinc, gallium, nickel, cobalt, molybdenum, tungsten, rhenium, rare earth elements, platinum group metals in an amount of no more than 10 Gt; %.

8. The method of claim 1. 5-7, characterized in that the catalyst in the second reactor is prepared by adding an additive by impregnation and / or by ion exchange at a temperature of more than 20 ° C., or by applying an additive from the gas phase, or by adding the additive by mechanical mixing with the starting material , Followed by drying and calcination of the resulting catalyst.

9. The method of claim 1. 5-8, characterized in that the process of conversion of gases in the second reactor is carried out at a temperature of 350-600 ° C and a pressure of not more than 2.5 MPa, with a weight flow rate of the gas mixture of not more than 5 h -1 .

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Date of publication 07.04.2007gg