A method of processing petroleum distillates (options)

 

(57) Abstract:

Usage: petrochemistry. The inventive processing of petroleum distillates to gasoline fraction with an end boiling point not higher than 195oAnd the octane number of at least 80 by the motor method consists in converting hydrocarbons in the presence of porous catalyst at a temperature of 250-500oC, a pressure of not more than 2 MPa, the mass expense of a mixture of hydrocarbons of not more than 10 h-1. As a source of raw materials use petroleum distillates with end boiling point 200-400oWith, and as a catalyst is used or zeolite aluminosilicate composition with a molar ratio of SiO2/A12ABOUT3not more than 450 selected from a number of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or gallosilikata, haloaluminate, gelatoria, telesolutions, prosilica, chromalusion with the structure of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or lumotast structure type ARO-5, ARO-11, ARO-31, ARO-41, ARO-36, ARO-37, ARO-40 introduced into the structure at the stage of synthesis of element selected from a number of: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium. The technical result is a simplification of the technology and increase the yield of target products. 3 S. and 9 C.p. f-crystals.

The invention otnositssya distillates.

There are several ways of producing high octane gasoline fractions from hydrocarbon material in the presence of catalysts. A method of obtaining high-octane gasoline by reforming of gasoline fractions of gas condensates [Shkuratov E. A., and others Receive high-octane gasoline catalytic reforming of gasoline fractions of condensates. In Proc. of Receiving and separation of the products of petrochemical synthesis. Krasnodar book. publishing house, 1974, S. 55-64].

According to this method, pre-allocated from the gas condensate fraction is initially subjected to deep catalytic hydrofining, drying the adsorbent, and then the reforming. The process is performed on aluminium oxide-platinum catalyst AP-64 at temperatures 480-510oC, a pressure of 3.5 MPa, the space velocity of the feedstock 1.5 h-1and circulation of hydrogen containing gas. This way you can receive high-octane gasoline fractions with PTS to 79-89 by the motor method (MM) and the output 79-89% on raw material reforming unit. The main disadvantages of this method are the complex technology of training materials for the process and application of hydrogen-containing gas.

A known method of producing motor fuels from fractions is of Ricci gas condensate in high-octane fuel. - Chemistry and technology of fuels and oils, 1988, No. 5, S. 6-7].

According to this method, high-octane gasoline is produced by Zeoforming of straight-run gasoline fractions allocated from gas condensates along with gas, straight-run diesel and residual fractions. The Zeoforming as follows: straight-run gasoline fraction separated with the separation of fractions of NC-58oAnd >58oWith the second fraction is subjected to contacting at elevated temperatures (up to 460oC) and pressure (5 MPa) with a zeolite-containing catalyst, the reaction products fractionary with the release of hydrocarbon gases, the residual fraction >195oAnd high-octane fraction <195With that compounding with a grain size of NC-58oTo retrieve the target gas. The main disadvantages of this method are the relatively low yields and octane number of gasolines produced.

The closest in technical essence and the achieved effect is a method of producing high octane gasoline from a gas condensate fractions [U.S. Pat. RF 2008323, C 10 G 51/04, 28.02.1994]. According to the prototype of stable gas condensate fractionary emitting trail is UP>With, and residual, wikipeida above 240oC. Residual fraction or its mixture with gaseous reaction products are subjected to pyrolysis at a temperature of 600-900oC. the Products of pyrolysis fractionary with gaseous and liquid fractions. The sin is blended with straight-run gasoline fraction and subjected to joint contact with the zeolite catalyst. Products contact fractionary emitting hydrocarbon gas and gasoline fractions, which compounder with pyrolysis condensate fraction and subjected to fractional distillation to isolate a target petrol FR. NC-195oAnd residual fractions >185oC. In this method outputs the target gasoline fraction is 46.8% in terms of stable gas condensate, or 82,4% straight-run gasoline fraction.

Thus, the main disadvantages of the method of producing high-octane gasoline that is closest to the proposed invention, are the complexity of the technology of producing high octane gasoline as a result of repeated fractionation of a mixture of hydrocarbons, as well as the relatively low yields of the target gasoline fractions in the calculation of the transformed raw materials.

The invention solves the problem by the creation of the military the yield of the target products high-octane gasoline fractions.

The problem is solved by a method of processing petroleum distillates to gasoline fraction with an end boiling point not higher than 195oAnd the octane number of at least 80 by the motor method, which consists in the conversion of hydrocarbons in the presence of porous catalyst at a temperature of 250-500oC, a pressure of not more than 2 MPa, the mass expense of a mixture of hydrocarbons of not more than 10 h-1while in feedstock use petroleum distillates with an end boiling point not higher than 400oAnd as the catalyst used zeolite aluminosilicate composition with a molar ratio of SiO2/Al2ABOUT3not more than 450 selected from a number of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA.

The second solution differs from the first by the fact that as the catalyst use gallosilikata, haloaluminate, gelatoria, telesolutions, prosilica, chromalusion with the structure of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA.

A third solution to the problem differs in that the catalyst used lumotast structure type l-5, l-11, l-31, l-41, l-36, l-37, l-40 introduced into the structure at the stage of synthesis of element selected from p is each variant of the method, may contain a compound of at least one of a number of metals: zinc, gallium, Nickel, cobalt, molybdenum, tungsten, rhenium, rare earth elements, platinum group metals in an amount of not more than 10 wt.%. The catalyst for each variant of the method is prepared by introducing additives by impregnation and/or ion exchange method at a temperature of more than 20oWith, or coating additives from the gas phase, or by the introduction of additives by mechanical mixing with the raw material, followed by drying and calcining.

Original oil distillate containing sulfur compounds in quantities not exceeding 10 wt.% in terms of elemental sulfur, is subjected to contacting with the catalyst without prior desulfurization.

The main distinguishing feature of the proposed method is that as a feedstock for producing high-octane gasoline used oil straight-run distillates wide hydrocarbon composition without prior fractionation emitting gas, straight-run gasoline, diesel and residual fractions and without preliminary purification from sulfur-containing compounds.

The technical effect of the proposed method zaklyuchitelnogo fractionation leads to simplification of the process, reducing the number of process steps and increase output of high-octane gasoline fractions in terms of straight-run gasoline fraction in the composition of petroleum distillates.

The method is as follows.

As starting material for the preparation of the catalyst used in this method use one of the materials selected from the row: or zeolites ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA with a molar ratio of SiO2/Al2O3not more than 450, galloylated and haloaluminate, relatoseroticos, zhelezohromovye, hamiliton, hromosomadelita with the structure of ZSM-5 and/or ZSM-11, ZSM-48, BETA, or alumophosphates with structures such as ALPO-5, - 11, - 31, - 41, - 36, - 37, - 40, with the introduction of the structure at the stage of synthesis of elements selected from a number of magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium.

Next, the source material if necessary, modify the introduction to his composition of at least one of the metals of the number of zinc, gallium, Nickel, cobalt, molybdenum, tungsten, rhenium, rare earth elements, platinum group metals in an amount of not more than 10 wt.%.

The modification of the zeolite is carried out by impregnation, activated impregnation in asterousia additive catalyst is dried and calcined at temperatures up to 600oC.

The catalyst is placed in a flow reactor, rinsed or nitrogen, or an inert gas or mixtures thereof at temperatures up to 600oWith, then served hydrocarbons when mass flows up to 10 h-1, temperatures of 250-500oC, a pressure of not more than 2 MPa.

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

Example 1. From a powder of zeolite ZSM-5 with a molar ratio of SiO2/Al2OC= 60 cook fraction 0,2-0,8 mm 5 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 500oC for 2 hours, then lower the temperature to 350oWith and stop the flow of nitrogen. Then, at this temperature and atmospheric pressure begin the filing of the original distillate NK-250oWith containing 0.5% sulfur content of the gasoline fraction was 79.1 wt. %, the estimated octane number for MM - 58,3), with the mass feed rate of 1.5 h-1. 2 hours after start of the reaction, the yield of gasoline fraction generated 60.9 wt.% (estimated octane number in MM 81,5), representing 77% of the gasoline fraction in the original distillate.

Example 2. 30 g of the powder of zeolite BETA with m38H2O. 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 sample obtained is dried at 100oC, calcined at 550oWith, then cook fraction of 0.2 to 0.8 mm, the Catalyst contains 0.7 wt.% gallium.

5 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 500oC for 2 hours, then lower the temperature to 350oWith and stop the flow of nitrogen. Then, at this temperature and atmospheric pressure begin the filing of the original distillate NC-300o(The content of the gasoline fraction was 69.7 wt.%, the estimated octane number for MM - 57,7) with the mass feed rate of 2.4 h-1. 2 hours after start of the reaction, the yield of gasoline fraction at 64.3 wt.% (estimated octane number for MM - 82,7) that is 92,3% of the gasoline fraction in the original distillate.

Example 3. Prepare a mechanical mixture of 30 g of gelatoria with the structure of ZSM-11 and 3 g WO3. The obtained sample annealed at 550oC for 4 hours, then cook fraction 0,2-0,8 mm

5 g of the obtained catalyst is placed in protocure 400oWith and stop the flow of nitrogen. Then, at this temperature and atmospheric pressure begin the filing of the original distillate NK-250oWith containing 0.5% sulfur content of the gasoline fraction was 79.1 wt.%, the estimated octane number for MM - 58,3), with the mass feed rate of 2.1 h-1. 2 hours after start of the reaction, the yield of gasoline fraction was 58.2 wt.% (estimated octane number in MM 84,5) that 73,6% of the gasoline fraction in the original distillate.

Example 4. 20 g of the aluminosilicate with the structure of ZSM-48 is blown with nitrogen containing pairs of molybdenum acetylacetonate at a temperature of 250oC. After the number passing through a sample of molybdenum acetylacetonate will match the content of molybdenum in the sample, 5%, stop the flow of nitrogen, the sample is rinsed with air at a temperature of 560oC for 2 hours. Then prepare the fraction of 0,2-0,8 mm

5 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 500oC for 2 hours, then lower the temperature to 350oWith and stop the flow of nitrogen. Then, at this temperature and a pressure of 0.8 MPa begin the filing of the original distillate NC-300oWith containing of 1.0% sulfur-1. 2 hours after start of the reaction, the yield of gasoline fraction amounted to 52.9 wt.% (estimated octane number for MM - 86,6), representing 81% of the gasoline fraction in the original distillate.

Example 5. 5 g of the catalyst from example 4 was placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 500oC for 2 hours, then lower the temperature to 350oWith and stop the flow of nitrogen. Then, at this temperature and atmospheric pressure begin the filing of the original distillate PC-300oWith containing 1.0 percent sulfur content of the gasoline fraction was 65.3 wt.%, the estimated octane number in MM 59,2), with the mass feed rate of 2.8 h-1. 2 hours after start of the reaction, the yield of gasoline fraction 60.2 wt.% (estimated octane number for MM - 81,8), representing 92.2% of the gasoline fraction in the original distillate.

Example 6. 30 g alumophosphate structure ARE-31 containing 1.4 wt.% Si, is introduced into the structure during hydrothermal synthesis, impregnated with a solution of Nickel nitrate based content of 1.5 wt.% Ni in the final catalyst. The catalyst was calcined for 2 hours at a temperature of 600oWith, then draw a fraction of 0,2-0,8 mm

10 g is received from the owls, then lower the temperature to 400oWith and stop the flow of nitrogen. Then, at this temperature and a pressure of 0.5 MPa begin the filing of the original distillate NC-300oWith containing 1.0 percent sulfur content of the gasoline fraction was 65.3 wt.%, the estimated octane number in MM 59,2), with the mass feed rate of 1.4 h-1. 2 hours after start of the reaction, the yield of gasoline fraction amounted to 57.7 wt.% (estimated octane number for MM - 84,1), representing 88.4% of the gasoline fraction in the original distillate.

Example 7. From powder allieluvslalo with the structure of ZSM-5 prepared fraction of 0.2 to 0.8 mm, 7 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 500oC for 2 hours, then lower the temperature to 350oWith and stop the flow of nitrogen. Then, at this temperature and atmospheric pressure begin the filing of the original distillate NK-350oWith containing 3,75% of the sulfur content of the gasoline fraction 53,1 wt.%, the estimated octane number in MM 61,0), with the mass feed rate of 1.3 h-1. 2 hours after start of the reaction, the yield of gasoline fraction was 52.4 wt.% (estimated octane number for MM - 88,3) that is 98,7% of the gasoline fraction in the outcome of the volume (5 l/h) at a temperature of 500oC for 2 hours, then lower the temperature to 350oWith and stop the flow of nitrogen. Then, at this temperature and a pressure of 1 MPa begin the filing of the original distillate NK-350oWith containing 3,75% of the sulfur content of the gasoline fraction 53,1 wt.%, the estimated octane number in MM 61,0), with the mass feed rate of 2.4 h-1. After 3 hours after start of the reaction, the yield of gasoline fraction was 54,0 wt.% (estimated octane number for MM - 85,6), which is of 101.7% of the gasoline fraction in the original distillate.

Example 9. 10 g of the catalyst from example 7 is placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 500oC for 2 hours, then reduce the temperature to 375oWith and stop the flow of nitrogen. Then, at this temperature and a pressure of 1 MPa begin the filing of the original distillate NK-350oWith containing 3,75% of the sulfur content of the gasoline fraction 53,1 wt.%, the estimated octane number in MM 61,0), with the mass feed rate of 2.7 h-1. 2 hours after start of the reaction, the yield of gasoline fraction was 62,0 wt.% (estimated octane number for MM - 84,6) that is 116,8% of the gasoline fraction in the original distillate.

Example 10. 7 g of the catalyst from PE then lower the temperature to 400oWith and stop the flow of nitrogen. Then, at this temperature and a pressure of 0.5 MPa begin the filing of the original distillate NK-350oWith containing 3,75% of the sulfur content of the gasoline fraction 53,1 wt.%, the estimated octane number in MM 61,0), with the mass feed rate of 2.8 h-1. After 3 hours after start of the reaction, the yield of gasoline fraction amounted to 60.3 wt.% (estimated octane number for MM - 82,7) that is 113,6% of the gasoline fraction in the original distillate.

The advantage of this method compared to known methods is that when the conversion of straight-run petroleum distillates without prior fractionation and preliminary purification from sulfur-containing compounds is achieved by increasing the output of high-octane gasoline fractions up to 117% (based on low-octane gasoline fraction in the original petroleum distillates. The use of different catalysts allows to obtain a gasoline fraction with different octane.

Receive high-octane gasoline fractions have the octane number by the motor method) not less than 80 and are ready motor fuel that does not require the introduction of high-octane additives, the content of sulfur in the POI 1 is impregnated with a solution of zinc acetate at the rate 2.5 wt.% Zn in the composition of the final catalyst. Thus obtained catalyst was calcined for 2 hours at a temperature of 550oC.

6 g of the prepared catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 500oC for 2 hours, then lower the temperature to 400oWith and stop the flow of nitrogen. Then, at this temperature and a pressure of 0.6 MPa begin the filing of the original distillate NC-300oWith containing 1.0 percent sulfur content of the gasoline fraction was 65.3 wt.%, the estimated octane number in MM 59,2), with the mass feed rate of 1.3 h-1. 2 hours after start of the reaction, the yield of gasoline fraction was 66.1 wt.% (estimated octane number in MM is 84.7), that is to 101.2% of the gasoline fraction in the original distillate.

Example 12. 50 g of gullibility with the structure of ZSM-5 pour 1 liter of an aqueous solution containing 30 g of lanthanum chloride. The resulting suspension is boiled with stirring and reflux for 3 hours, after which the powder is separated on a filter, washed with distilled water and dried. The sample obtained is dried at 100oC, calcined at 550oWith, then cook fraction of 0.2 to 0.8 mm, the Catalyst contains 0.6% of lanthanum.

10 g of the obtained catalyst is about lower the temperature to 400oWith and stop the flow of nitrogen. Then, at this temperature and a pressure of 0.7 MPa begin the filing of the original distillate NK-350oWith containing 3,75% of the sulfur content of the gasoline fraction 53,1 wt.%, the estimated octane number in MM 61,0), with the mass feed rate of 1.2 h-1. 2 hours after start of the reaction, the yield of gasoline fraction was 59,0 wt.% (estimated octane number for MM - 87,7), that is by 115.7% of the gasoline fraction in the original distillate.

Example 13. 30 g zhelezohromovye with the structure of ZSM-48 is mechanically mixed with tungsten oxide 4 wt.% tungsten in the composition of the final catalyst. The catalyst was calcined for 2 hours at a temperature of 500oWith, then draw a fraction of 0,2-0,8 mm

10 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 500oC for 2 hours, then reduce the temperature to 375oWith and stop the flow of nitrogen. Then, at this temperature and a pressure of 0.4 MPa begin the filing of the original distillate NC-300oWith containing 1.0 percent sulfur content of the gasoline fraction was 65.3 wt.%, the estimated octane number in MM 59,2), with the mass feed rate of 1.1 h-1. 2 hours after the beginning of the Rea is inovas fraction in the original distillate.

Example 14. 40 g hromosomadelita with the structure of ZSM-35 is mechanically mixed with gallium nitrate from the calculation of 3.0 wt.% gallium in the composition of the final catalyst. The catalyst was calcined for 2 hours at a temperature of 500oWith, then draw a fraction of 0,2-0,8 mm

10 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 500oC for 2 hours, then lower the temperature to 400oWith and stop the flow of nitrogen. Then, at this temperature and a pressure of 0.4 MPa begin the filing of the original distillate NK-350oWith containing 3,75% of the sulfur content of the gasoline fraction 53,1 wt.%, the estimated octane number in MM 61,0), with the mass feed rate of 1.6 h-1. 2 hours after start of the reaction, the yield of gasoline fraction was 59,0 wt.% (estimated octane number for MM - 84,8) that is 111,1% of the gasoline fraction in the original distillate.

Example 15. 35 g of marialuisa structure ARE-36, containing 1.2 wt.% Mg introduced into the structure during hydrothermal synthesis, mechanically mixed with acetate of cobalt based content of 2.5 wt.% With in the final catalyst. The catalyst was calcined for 2 hours at a temperature of 550ooC for 2 hours, then lower the temperature to 425oWith and stop the flow of nitrogen. Further, when the temperature and pressure of 1.0 MPa begin the filing of the original distillate NC-300oWith containing 1.0 percent sulfur content of the gasoline fraction was 65.3 wt.%, the estimated octane number in MM 59,2), with the mass feed rate of 1.6 h-1. 2 hours after start of the reaction, the yield of gasoline fraction was of 62.4 wt.% (estimated octane number for MM - 82,9), representing 95.6% of the gasoline fraction in the original distillate.

Example 16. 20 g of silicoaluminate structure ARE-37 containing 3.4 wt. % Si, is introduced into the structure during hydrothermal synthesis, mechanically mixed with tungsten oxide WO3from the calculation of the content of 1.2 wt.% W in the final catalyst. The catalyst was calcined for 2 hours at a temperature of 500oWith, then draw a fraction of 0,2-0,8 mm

10 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 500oC for 2 hours, then lower the temperature to 400oWith and stop the flow of nitrogen. Then, at this temperature and a pressure of 0.4 MPa begin the filing of the original words in MM - 61,0), with the mass feed rate of 1.2 h-1. 2 hours after start of the reaction, the yield of gasoline fraction was 57.1 wt.% (estimated octane number in MM 85,0), that is to 107.5% of the gasoline fraction in the original distillate.

Example 17. 30 g telesolutions structure ARO-5, containing 1.6 wt.% Fe, introduced into the structure during hydrothermal synthesis, is subjected to ion exchange in a solution of Nickel nitrate for 26 hours at room temperature. The catalyst is washed in distilled water, air-dried and calcined for 2 hours at a temperature of 550oC. the Nickel Content in the final catalyst is 0.8 wt.%. Of the catalyst prepared fraction 0,2-0,8 mm

10 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 500oC for 2 hours, then lower the temperature to 400oWith and stop the flow of nitrogen. Then, at this temperature and a pressure of 0.6 MPa begin the filing of the original distillate NC-300oWith containing 1.0 percent sulfur content of the gasoline fraction was 65.3 wt.%, the estimated octane number in MM 59,2), with the mass feed rate of 1.2 h-1. 2 hours after start of the reaction, the yield of gasoline proxhodova distillate.

Example 18. 30 g silicoaluminate structure ARO-40, containing 3.4 wt. % Si, is introduced into the structure during hydrothermal synthesis, impregnated with a solution of lanthanum nitrate based content of 2.0 wt.% La in the final catalyst. The catalyst was calcined for 2 hours at a temperature of 550oWith, then draw a fraction of 0,2-0,8 mm

10 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 600oC for 2 hours, then lower the temperature to 400oWith and stop the flow of nitrogen. Further, when the temperature and pressure of 1.0 MPa begin the filing of the original distillate NC-300oWith containing 1.0 percent sulfur content of the gasoline fraction was 65.3 wt.%, the estimated octane number in MM 59,2), with the mass feed rate of 1.6 h-1. 2 hours after start of the reaction, the yield of gasoline fraction amounted to 60.6 wt.% (estimated octane number for MM - 81,3), representing 92.8% of the gasoline fraction in the original distillate.

Example 19. 35 g of silicoaluminate structure ARE-41 containing 1.5 wt. % Si, is introduced into the structure during hydrothermal synthesis, rinsed with nitrogen, containing a pair of molybdenum acetylacetonate at a temperature of 250oWhen the neigh of molybdenum in the sample, 5%, stop the flow of nitrogen, the sample is rinsed with air at a temperature of 550oC for 2 hours. Then prepare the fraction of 0,2-0,8 mm

5 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 500oC for 2 hours, then lower the temperature to 450oWith and stop the flow of nitrogen. Then, at this temperature and a pressure of 0.4 MPa begin the filing of the original distillate NK-350oWith containing 3,75% of the sulfur content of the gasoline fraction 53,1 wt.%, the estimated octane number in MM 61,0), with the mass feed rate of 1.3 h-1. 2 hours after start of the reaction, the yield of gasoline fraction was 55.6 wt.% (estimated octane number in MM - to 85.2), that is 104.7% of the gasoline fraction in the original distillate.

Example 20. 10 g of cobalttsumcorite structure ARE-11 in the form of fractions of 0.2-0.8 mm are placed in a reactor, rinsed with nitrogen (5 l/h) at a temperature of 500oC for 2 hours, then lower the temperature to 450oWith and stop the flow of nitrogen. Then, at this temperature and a pressure of 0.8 MPa begin the filing of the original distillate NK-350oWith containing 3,75% of the sulfur content of the gasoline fraction 53,1 wt.%, the estimated octane number put 54,9 wt.% (estimated octane number in MM - 87,0) that is 103,4% of the gasoline fraction in the original distillate.

Example 21. 30 g cadiologist structure ARE-31 is impregnated with a solution of zinc acetate at the rate 2.5 wt.% zinc in the composition of the final catalyst. The catalyst was calcined for 2 hours at a temperature of 550oWith, then draw a fraction of 0,2-0,8 mm

10 g of the obtained catalyst is placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 600oC for 2 hours, then lower the temperature to 450oWith and stop the flow of nitrogen. Further, when the temperature and pressure of 1.0 MPa begin the filing of the original distillate NC-300oWith containing 1.0 percent sulfur content of the gasoline fraction was 65.3 wt.%, the estimated octane number in MM 59,2), with the mass feed rate of 1.5 h-1. 2 hours after start of the reaction, the yield of gasoline fraction accounted for 66.7 wt.% (estimated octane number in MM 85,0) that is 102,1% of the gasoline fraction in the original distillate.

1. A method of processing petroleum distillates to gasoline fraction with an end boiling point not higher than 195oWith and octane rating below 80 by the motor method, which consists in the conversion of hydrocarbons in prisutstvovatb no more than 10 h-1, characterized in that the feedstock used petroleum distillates with end boiling point 200-400oAnd as the catalyst used zeolite aluminosilicate composition with a molar ratio of SiO2/Al2O3not more than 450 selected from a number of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA.

2. The method according to p. 1, characterized in that the catalyst 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 not more than 10 wt. %.

3. The method according to PP. 1 and 2, characterized in that the catalyst is prepared by introducing additives by impregnation and/or ion exchange method at a temperature of more than 20oWith, or coating additives from the gas phase, or by the introduction of additives by mechanical mixing with the raw material, followed by drying and calcining of the resulting catalysts.

4. The method according to PP. 1 to 3 characterized in that the source of petroleum distillates containing sulfur compounds in quantities not exceeding 10 wt. % in terms of elemental sulfur, is subjected to contacting with the catalyst without prior desulfurization.

5. A method of processing oil on the method consisting in the conversion of hydrocarbons in the presence of porous catalyst at a temperature of 250-500oC, a pressure of not more than 2 MPa, the mass expense of a mixture of hydrocarbons of not more than 10 h-1, characterized in that the feedstock used petroleum distillates with end boiling point 200-400oWith, and as a catalyst for use gallosilikata, haloaluminate, gelatoria, telesolutions, prosilica, chromalusion with the structure of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA.

6. The method according to p. 5, characterized in that the catalyst 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 not more than 10 wt. %.

7. The method according to PP. 5 and 6, characterized in that the catalyst is prepared by introducing additives by impregnation and/or ion exchange method at a temperature of more than 20oWith, or coating additives from the gas phase, or by the introduction of additives by mechanical mixing with the raw material, followed by drying and calcining of the resulting catalysts.

8. The method according to PP. 5 to 7, characterized in that the source of petroleum distillates containing stylization without prior desulfurization.

9. A method of processing petroleum distillates to gasoline fraction with an end boiling point not higher than 195oAnd the octane number of at least 80 by the motor method, which consists in the conversion of hydrocarbons in the presence of porous catalyst at a temperature of 250-500oC, a pressure of not more than 2 MPa, the mass expense of a mixture of hydrocarbons of not more than 10 h-1, characterized in that the feedstock used petroleum distillates with end boiling point 200-400oWith, and as a catalyst for use lumotast structure type ARO-5, ARO-11, ARO-31, ARO-41, ARO-36, ARO-37, ARO-40 introduced into the structure at the stage of synthesis of element selected from a number of: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium.

10. The method according to p. 9, characterized in that the catalyst 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 not more than 10 wt. %.

11. The method according to PP. 9 and 10, characterized in that the catalyst is prepared by introducing additives by impregnation and/or ion exchange method at a temperature of more than 20oWith, or coating additives from the gas phase, or wnich catalysts.

12. The method according to PP. 9 to 11, characterized in that the source of petroleum distillates containing sulfur compounds in quantities not exceeding 10 wt. % in terms of elemental sulfur, is subjected to contacting with the catalyst without prior desulfurization.

 

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The invention relates to methods of producing aromatic hydrocarbons from a hydrocarbon and can be used in the refining and petrochemical industry for the processing of gases containing paraffins and olefins, C2-C4and various gasoline fractions into high-octane gasoline, enriched compared with the raw material aromatic hydrocarbons, and also the concentrate of aromatic hydrocarbons

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

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