Gasoline and diesel fuel production process

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

 

The invention relates to the processing of various hydrocarbons, namely, gas condensates and petroleum distillates with an end boiling point not higher than 400°in high-octane gasoline, diesel fuel with a low freezing point.

In the scientific and patent literature does not describe processes, target products which at the same time would be waxy diesel fuel, high-octane unleaded gasoline and concentrate of aromatic compounds. Meanwhile, all three of these components are the most valuable and scarce products of any hydrocarbons. In Russia the production of unleaded gasoline having octane number determined by the research method 95 and above for 2001 amounted to only 5% of the total gasoline production [Som V.E., Sadchikov I.A., Shershun VG, Karaskov L.V. Strategic priorities of Russian oil refineries, JSC "Tsniiteneftehim", Moscow, 2002, P.57]. The proportion of waxy diesel fuels (total marks DZ and DA) in the total production of diesel fuel in Russia is 13%, with the existing requirements in 35% [ibid, p.63]. Aromatic compounds are not less valuable products than motor fuel. So, currently, the share of arenes accounting for 21% of the world's petrochemical products [Weirauch is. Oil and gas technology, 1996, No. 6, P.46].

In the patent literature there are descriptions of the processes that produced two of the three above products. As a rule, it is the joint production of gasoline and diesel fuel.

A method of obtaining high-octane gasoline and diesel fuel fractions of gas condensate [U.S. Pat. RF 2008323, C 10 G 51/04, 28.02.1994]. According to this method, stable gas condensate fractionary with the release of the following straight-run fractions: petrol, wikipeida to 140-200°C, diesel, wikipeida within form 140 to 340°and residual, wikipeida above 340°C. the Residual fraction or its mixture with gaseous reaction products are subjected to pyrolysis at a temperature of 600-900°C. the pyrolysis Products fractionary with gaseous and liquid fractions. The sin is blended with straight-run gasoline fraction and subjected to contacting with a zeolite-containing 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-195°and residual fractions >185°C. the resulting diesel fuel is a typical straight-run fuel has a freezing point of not lower than -10°and may not use what to use in the cold season.

The main disadvantages of this method 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 high pour point of the resulting diesel fuel. In addition, in this way a significant amount of liquid hydrocarbons turns into a gas having a relatively low consumer value.

A method of refining petroleum distillates [U.S. Pat. RF N 2181750, C 10 G 35/095, 19.04.2001]. According to this method, a petroleum distillate with an end boiling point not more than 400°containing sulfur compounds in quantities not exceeding 10 wt.% in terms of elemental sulfur, at a temperature of 250-500°C, pressure of not more than 2 MPa, mass flow rate of the raw material is not more than 10 h-1in contact with a porous catalyst, which is used as the 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. In this way the main products are gasoline with an octane rating no lower than 80 by the motor method and diesel fuel with a pour point of not more than minus 35°C. in Addition to these products is formed, a gas containing fraction With3-C4and also a certain amount of hydrogen sulfide gas and dry gas (C1-C2). Total in the gas flow reaches 18 wt.% in the calculation of the supplied raw materials.

The main disadvantage of this method is the reduction of the yield of liquid motor fuels in terms of transformed raw materials, caused by the transformation of some part of the liquid raw material in a gaseous under normal conditions the products.

The closest in technical essence and the achieved effect is a method of processing petroleum distillates [U.S. Pat. RF N 2216569, C 10 G 35/095, 35/04, 30.10.2002]. According to this method, the hydrocarbon feedstock is transformed into high-octane gasoline and waxy diesel fuel in the presence of porous catalyst at a temperature of 250-500°C, pressure of not more than 2.5 MPa, mass flows of a mixture of hydrocarbons of not more than 10 h-1at the same time as the feedstock use of hydrocarbon distillates of different origin with end boiling point not higher than 400°and as a catalyst for use zeolite aluminosilicate with molinism ratio of SiO2/Al2O3not 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 with the structure of AlPO-5, AlPO-11, AlPO-31, AlPO-41, AlPO-36, AlPO-37, AlPO-40 entered in the structure at the stage of synthesis of element selected from a number of: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium. At the exit of the reactor products are divided into petrol, diesel and gas fraction. Then the gas is sent to the second reactor, a catalyst containing a 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, or gallosilikata, haloaluminate, gelatoria, telesolutions, prosilica, chromalusion with the structure of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or lumotast with the structure of AlPO-5, AlPO-11, AlPO-31, AlPO-41, AlPO-36, AlPO-37, AlPO-40 entered in the structure at the stage of synthesis of element selected from a number of: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium. The process of turning gas is conducted at a temperature of 300-600°C, pressure up to 2.5 MPa and weight gas flow rate of 0.1-5 h-1. In the second reactor serves or all of the gas from the first reactor without separation of individual components or of the gas into the hydrocarbon component of C1-C4, which is sent to the second reactor, or from the gas emit only a fraction With the3-C4that served in the second reactor. The liquid products formed in the second reactor is mixed with the gasoline fraction from the first reactor.

The main disadvantage of this method is the relatively low yield of liquid motor fuels (average of 87.5 wt.%), and also appreciated the content in gasoline hydrocarbons With 5. The average octane number of these compounds does not exceed 77 by the motor method. To compensate for the influence of this low-octane component is increased in the composition of the gasoline content of high-octane aromatic compounds due to tightening mode (temperature increase and reduction of consumption of raw materials) in the first reactor, which leads to increased gas production. In addition, the resulting gasoline aromatic content no longer fit within GOST 51866-2002, whereby the concentration of aromatic compounds in gasoline should not exceed 42%vol.

The present invention solves the problem of creating improved method of producing motor fuels, allowing higher outputs liquid products and is characterized by producing high-octane gasoline with aromatic content not more than 42% vol. and diesel fuel with a pour point of not higher than -35°With the octane number of the produced gas, at least not compared with the prototype - at least 83 (motor method). In addition, one of the options in the claimed process produces a significant amount of aromatic compounds that can be used either as a high-octane additive for the compounding of low-octane gasoline, or as a valuable raw material is La petrochemicals.

The problem is solved in three variants of the method of processing of hydrocarbons in the gasoline with end boiling point not higher than 210°and With an octane rating no lower than 83 by the motor method, and diesel fuel with a pour point of not higher than -35°consisting in the conversion of hydrocarbons in the presence of porous catalyst at a temperature of 250-500°C, pressure of not more than 2.5 MPa, mass flows of a mixture of hydrocarbons of not more than 10 h-1at the same time as the feedstock use of hydrocarbon distillates of different origin with end boiling point not higher than 400°and as a catalyst for use 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, or gallosilikata, haloaluminate, gelatoria, telesolutions, prosilica, chromalusion with the structure of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA 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 main otricatelniy characteristic of the proposed method is that formed during the reaction products are separated in a separator under such conditions that the hydrocarbons5remain in the gas phase with gaseous under normal conditions, the carbohydrate is childbirth C 1-C4. When the separator at atmospheric pressure and the temperature of the flow of hydrocarbons 40°With an optimum content of hydrocarbons With5in the gas phase. The temperature increase and pressure decrease leads to an unnecessary increase in the gas phase hydrocarbon content6+, lowering the temperature and increasing the pressure leads to a decrease in the gas concentration of the hydrocarbons With5. Next, the resulting mixture of hydrocarbon, C1-C5processed in the second reactor to form additional quantities of liquid products, namely concentrate of aromatic compounds.

The first solution is depicted in figure 1 (Figure 1), where P1oven first reactor; P2- bake the second reactor; P1, R2reactors; C1C2- separators; To the column.

The method consists in the fact that the process of producing motor fuels in the first reactor is carried out under such conditions that the resulting gasoline is finished motor fuel and does not require octane additives. In this case, after the separation in high-temperature separator from a mixture of gasoline and diesel fuel fraction of hydrocarbons With1-C5sent to the second reactor, a catalyst containing a zeolite aluminosilicate with molny the ratio of SiO 2/Al2About3not 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 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 process of converting fractions C1-C5carried out at a temperature of 300-600°C, at pressures up to 2.5 MPa, and a weight rate of 0.1-5 h-1.

At the outlet of the second reactor products share gas consisting mainly of methane and ethane (C1+C2a total of more than 80 wt.%), and liquid products, representing a concentrate of aromatic hydrocarbons total aromatic content6-C9more than 95 wt.%. The resulting gas is used to heat the digesters, and the concentrate of aromatic compounds used as solvents or petrochemical feedstock.

The catalyst used in the second reactor may contain a compound of at least one of a number of metals: zinc, gallium, Nickel, cobalt, molybdenum, tungsten, rhenium, rare earth element 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 in temp is the temperature more than 20° With 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.

The second way of solving the problem presented in figure 2 (Figure 2), where: R1oven first reactor; P2- bake the second reactor; P1P2reactors; C1C2- separators; column; bldg - site compounding.

It differs from the first by the fact that during the production of motor fuels in the first reactor is carried out under such conditions that the resulting gasoline is not high octane. In this case, the concentrate of aromatic compounds obtained in the second reactor of a mixture of hydrocarbons, C1-C5mixed with the gasoline fraction from the first reactor in the proportions necessary to produce gasoline with the desired octane number.

A third solution to the problem is presented in figure 3 (Figure 3) and differs from the first two by the fact that prior to being fed into the first reactor feedstock separate part of the gasoline fraction, then the conversion of the remaining part of the raw material is carried out similarly to the first two options. Clubbed originally part of the gasoline fraction further compounding products conversion of fraction C1-C5in the second reactor with the production of gasoline with the desired octane number.

The technical effect of the offer is the procedure consists of the following elements.

1. In case of separation of products from the first reactor hydrocarbon fractions C1-C5and use of the products of its transformation in the second reactor for compounding of gasoline, or straight, or obtained in the first reactor, the process of converting hydrocarbons in the first reactor should be maintained at less high temperature and at a higher consumption of raw materials in comparison with the prototype, which leads to a considerable increase in the yield of liquid products of the process. While the octane number of the produced gas, at least not lower than in the known method.

2. When the conversion in the second reactor fraction C1-C5of the products with a relatively low cost, are formed valuable aromatic compounds, which are used either for compounding of additional quantities of low-octane fuel or as a feedstock for petrochemicals.

3. The process in the first and second reactors at lower temperatures compared to the prototype leads to significant fuel savings.

In General, in the inventive process, the average yield of liquid products (total gasoline and diesel fuel, or gasoline, diesel fuel and concentrate aromatic compounds) always exceeds 90 wt.%, while in the prototype, the average yield of liquid products in all Pref is established examples equal to 87.5 wt.%.

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 range 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 introduced into 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 element in an amount of not more than 10 wt.%.

The modification of the zeolite is carried out by impregnation, activated impregnation autoclave, deposition from the gas phase, ion exchange, mechanical mixing of the components. After the introduction of the modifying additive, the catalyst was dried and calcined at temperatures up to 600°C.

The catalyst is placed in a flow reactor, rinsed or nitrogen, or inertnet gas or mixtures thereof at temperatures up to 600°With, then deliver liquid hydrocarbon raw materials in bulk costs up to 10 h-1

After exiting the reactor products after cooling in the refrigerator and pressure release to atmospheric fed into the separator, where the separation into gas and liquid components. The separator operates under steady-state conditions: the temperature of the flow of hydrocarbons 40°C, atmospheric pressure. Under these conditions the major part of the hydrocarbons5remains in the gas phase.

The liquid products of distillation are divided into gasoline and diesel fuel, and hydrocarbon, C1-C5(gases and the fraction of NK-40° (C) after the separator is directed to the second reactor filled with a catalyst selected from a number of 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 introduced into the structure at the stage of synthesis of elements selected from a number of magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium.

Thus the catalyst may further comprise a connection, at least one of the metals of the number of zinc, gallium, Nickel, cobalt, molybdenum, tungsten, rhenium, rare earth element in an amount of not more than 10 wt.%. Additive in the catalyst introduced by impregnation and/or m the method of ion exchange at a temperature of more than 20° With, or applied from the gas phase, or imposed by mechanical mixing with ishodnym material, followed by drying and calcining.

Loaded into the second reactor, the catalyst was pre-rinsed or nitrogen, or hydrogen, or methane, or dry gas, or inert gas or mixtures thereof at temperatures up to 600°S, and then at a temperature of 300-600°and With a pressure not more than 2.5 MPa begin to supply light products first reactor hydrocarbon, C1-C5while the weight flow rate of the raw material through the second reactor is in the range of 0.1 to 5 h-1.

At the outlet of the second reactor products come into the separator where it is separated into liquid and gas fractions. The resulting gas is used to heat the reactor, and the liquid fraction, representing a concentrate of aromatic hydrocarbons, in the first embodiment of the method is used as a petrochemical feedstock. Option is depicted in figure 1 (Figure 1).

According to the second variant of the method of liquid products obtained in the second reactor is mixed with the gasoline produced in the first reactor in accordance with scheme 2 (Figure 2).

In the third variant of the method shown in scheme 3 (Fig 3), the liquid products of the second reactor is mixed with straight-run gasoline fraction is removed from the feedstock prior to the first reactor.

The invention illyustriruyuschie examples.

Example 1. From a powder of zeolite ZSM-5 with a molar ratio of SiO2/Al2O3=70 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 500°C for 2 h, then lower the temperature to 345°and stop the flow of nitrogen. Then, at this temperature and atmospheric pressure begin the filing of the original distillate NK-250°mass feed rate of 1.75 h-1. At the exit of the reactor, the products are cooled to 40°and share in the separator liquid and gas phase, the liquid phase is collected for 8 h, then dispersed for gasoline NC-210°and diesel fuel. The gas containing the hydrocarbon, C1-C5directed to the second reactor filled with a catalyst prepared from a powder of zeolite ZSM-5 with molinism ratio of SiO2/Al2O3=50, in which the impregnation introduced to 1.5 wt.% Zn, the catalyst is pre-heated in a stream of nitrogen at 550°C. the Temperature in the second reactor 545°C, a pressure of 1.0 MPa, a weight consumption of raw materials 2.5 h-1. At the outlet of the second reactor, the products are separated in a separator for gaseous products and a concentrate of aromatic compounds.

In this mode of operation, the average yield of gasoline fraction is accounted for 71.3 wt.% when the octane number MM 88,5, the output of diesel fuel to 12.0 wt.%, temp is the temperature of solidification -49° C, the yield of liquid product of the second reactor to 8.2 wt.% when the concentration of aromatic hydrocarbons With6-C995.5%of the total yield of liquid products of 91.5 wt.% in the calculation of the supplied raw materials.

Example 2. 30 g of the powder of zeolite BETA with a molar ratio of SiO2/Al2O3=26 pour 1 liter of an aqueous solution containing 15 g of Ga(NO3)3HN2O. the resulting suspension is boiled with stirring and reflux 4 h, after which the powder is separated on a filter, washed repeatedly with distilled water and dried. The sample obtained is dried at 100°C, calcined at 550°With, 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 500°C for 2 h, then lower the temperature to 340°and stop the flow of nitrogen. Then, at this temperature and atmospheric pressure begin the filing of the original distillate NC-300°mass feed rate of 2.4 h-1.

Further separation of the products carried out analogously to example 1. The fraction of hydrocarbons, C1-C5served in the second reactor is filled with the same catalyst as the first. The temperature in the reactor 520°C, a pressure of 0.5 MPa, the weight of the feedstock flow rate of 2.0 h-1. At the outlet of the second reactor products share in Sep is the operator for the gaseous products and a concentrate of aromatic compounds.

The average yield of gasoline fraction is to 69.9 wt.%, the octane number in MM 87,5, diesel yield of 16.3 wt.%, the freezing point of -47°exit concentrate of aromatic hydrocarbons of 5.8 wt.%. The total yield of liquid hydrocarbons is 92,0 wt.%.

Example 3. 5 g of the catalyst of example 1 is placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 500°C for 2 h, then lower the temperature to 340°To stop the flow of nitrogen. Then, at this temperature and atmospheric pressure begin the filing of the original distillate NC-400°mass feed rate of 1.3 h-1. At the exit of the reactor, the products are cooled to 40°and share in the separator liquid and gas phase, the liquid phase is collected and dispersed as in example 1. Gases With1-C5passed through the second reactor, in which the downloaded prosilica, pre-treated at 250°With nitrogen, saturated vapors of zinc acetylacetonate at the rate of 3 wt.% zinc in the catalyst and activated 2 hours in a stream of air at 550°and 2 h in a stream of nitrogen at the same temperature. The temperature in the reactor 500°C, a pressure of 0.5 MPa, the weight flow rate of the raw material 1.75 h-1. At the exit of the reactor to the separator to separate the fraction of NC-210°With which is mixed with the gasoline fraction from the first reactor. The overall yield of gasoline fraction composition is yet to 66.5 wt.%, the octane number for MM - 88,0, diesel yield of 26.5 wt.%, the pour point of -46°C. the Total yield of liquid hydrocarbons is 93.0 wt.%.

Example 4. Prepare a mechanical mixture of 30 g of gelatoria with the structure of ZSM-11 and 4.5 g WO3. The obtained sample annealed at 550°C for 4 h, after which 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 500°C for 2 h, then lower the temperature to 390°and stop the flow of nitrogen. Then, at this temperature and atmospheric pressure begin the filing of the original distillate NK-350°mass feed rate of 2.1 h-1. Further separation of the products carried out analogously to example 1. Fraction With1-C5served in the second reactor filled with a catalyst prepared from a powder of zeolite ZSM-5 with a molar ratio of SiO2/Al2O3=50, impregnated wodnym solution of ammonium perrhenate NH4ReO4based 1,0 wt.% rhenium in the catalyst, followed by drying and calcining at 600°C. the Weight flow rate of the raw material through the second reactor 1,2 h-1temperature 500°C, atmospheric pressure. At the outlet of the second reactor liquid products separated in the separator and is mixed with the gasoline fraction obtained in the first reactor.

In this case, o is on gasoline is to 74.5 wt.%, the octane number for MM - 86,2, diesel yield of 18.2 wt.%, pour point -45°C. the Total output of motor fuels of 92.7 wt.%.

Example 5. 20 g of the aluminosilicate with the structure of ZSM-48 is blown with nitrogen containing pairs of molybdenum acetylacetonate at a temperature of 250°C. After the number passing through a sample of molybdenum acetylacetonate will match the content of molybdenum in the sample with 5 wt.%, stop the flow of nitrogen, the sample is rinsed with air at a temperature of 560°C for 2 hours Then 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 500°C for 2 h, then lower the temperature to 350°and stop the flow of nitrogen. Then, at this temperature and a pressure of 2.5 MPa begin the filing of the original distillate NC-300°mass feed rate of 1.4 h-1. At the exit of the reactor pressure dropped to atmospheric and the products are cooled to 40°With further separation of the products and the conversion of fraction C1-C5in the second reactor is carried out analogously to example 3. Obtained in the second reactor liquid products mixed with the gasoline fraction obtained in the first reactor.

In this case, the yield of gasoline fraction is 77.4 wt.%, the octane number in MM 87,5, diesel yield of 14.6 wt.%, pace is the atur solidification -56° C. the Total output of motor fuels 92 wt.%.

Example 6. 5 g of catalyst according to example 4 is placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 500°C for 2 h, then lower the temperature to 350°and stop the flow of nitrogen. From the original distillate NC-400 With distilled off 20% vol. straight-run gasoline fraction, which is sent on the node compounding. The remaining portion of the distillate with the mass feed rate of 3.8 h-1served in the flow reactor. Further separation of the products and the conversion of fraction C1-C5in the second reactor is carried out analogously to example 4. Liquid products obtained in the second reactor, mixed on site compounding with straight-run gasoline fraction with obtaining gasoline marked gasoline 2.

In this case, the output of gasoline after the first reactor is a 50.5 wt.%, the octane number for MM - 89,2, the output of gasoline 2 is to 22.0 wt.% when the octane number MM -85,5, diesel yield of 20.2 wt.%, pour point -50°C. the Total output of motor fuels of 92.7 wt.%.

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 500°C for 2 h, then lower the temperature to 350°and stop the flow of nitrogen. Further, when attemperator and a pressure of 2 MPa begin with the mass rate of 1.3 h -1the filing of the original distillate NC-400°from which whisked 15% vol. gasoline fraction. At the exit of the reactor pressure dropped to atmospheric, the products are cooled to 40°and share in the separator liquid and gas phase, the liquid phase is collected and dispersed as in example 1. The gas is then fed to the input of the second reactor filled with a catalyst based on zeolite ZSM-5, prepared and activated as in example 1. The temperature in the second reactor 550°C, atmospheric pressure, catalyst loading corresponds to the weight flow rate of the gas mixture 3 h-1. At the outlet of the second reactor liquid products separated in the separator and is mixed with the gasoline fraction, removed from the original distillate and gasoline produced in the first reactor.

In this mode of operation, the overall yield of gasoline fraction is only 68.6 wt.%, the octane number for MM - 88,0, diesel yield of 24.5 wt.%, pour point -53°C. the Total output of motor fuels br93.1 wt.%.

Example 8. 5 g of catalyst according to example 2 (based on zeolite BETA, promoted Ga) is placed in a flow reactor, rinsed with nitrogen (5 l/h) at a temperature of 500°C for 2 h, then lower the temperature to 350°and stop the flow of nitrogen. Then, at this temperature and a pressure of 1 MPa begin the filing of the original distillate NK-250°SS mass feed rate of 2.4 h -1. At the exit of the reactor pressure dropped to atmospheric, the products are cooled to 40°and share in the separator liquid and gas phase, the liquid phase is collected and dispersed as in example 1. The gas containing the hydrocarbon, C1-C5directed to the second reactor filled with a catalyst prepared from a powder of zeolite ZSM-5 with a molar ratio of SiO2/Al2O3=50, in which the impregnation introduced to 1.5 wt.% Ga, the catalyst is pre-heated in a stream of nitrogen at 550°C. the Temperature in the second reactor 545°C, a pressure of 1.0 MPa, the weight flow rate of the raw material 1.5 h-1. At the outlet of the second reactor liquid products separated in the separator and is mixed with the gasoline fraction obtained in the first reactor.

In this mode of operation, the overall yield of gasoline fraction is 81,1 wt.%, the octane number for MM to 90.0, diesel yield of 11.0 wt.%, pour point -48°C. the Total yield of liquid products of 92.1 wt.%.

Example 9. Powder of zeolite ZSM-5 with a molar ratio of SiO2/Al2O3=70 impregnated with an aqueous solution of La(NO3)3×6N2O calculation of 2.0 wt.% lanthanum in the catalyst, the sample annealed at 550°S, next, 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 500°for the of 2 h, then lower the temperature to 345°and stop the flow of nitrogen. Then, at this temperature and atmospheric pressure begin the filing of the original distillate NK-360°mass feed rate of 2.25 h-1. At the exit of the reactor, the products are cooled to 40°and share in the separator liquid and gas phase, the liquid phase is then dispersed in the gasoline NC-210°and diesel fuel. Gas containing hydrocarbons With1-C5directed to the second reactor filled with catalyst, prigotovlennym from a powder of zeolite ZSM-5 with a molar ratio of SiO2/Al2O3=50, in which the impregnation introduced to 1.5 wt.% With, the catalyst is pre-heated in a stream of nitrogen at 550°C. the Temperature in the second reactor 540°C, a pressure of 1.0 MPa, the weight of the feedstock flow rate of 2.3 h-1. At the outlet of the second reactor, the products are separated in a separator for gaseous products and a concentrate of aromatic compounds.

In this mode of operation, the average yield of gasoline fraction is 65,5 wt.% when the octane number MM 83,5, diesel yield of 19.2 wt.%, pour point -54°C, the yield of liquid product of the second reactor to 7.7 wt.% when the concentration of aromatic hydrocarbons With6-C996,2%, the total yield of liquid products to 92.4 wt.% in the calculation of the supplied raw materials.

As seen from the above exampl is, in the inventive process, the average yield of liquid products (total gasoline and diesel fuel, or gasoline, diesel fuel and concentrate aromatic compounds) always exceeds 90 wt.%, whereas in the known method, the average yield of liquid products in all these examples does not exceed of 87.5 wt.%.

1. The method of producing gasoline with an octane rating no lower than 83 by the motor method and diesel fuel with a pour point of not higher than -35°consisting in the conversion of hydrocarbons in the presence of porous catalyst at a temperature of 250-500°C, pressure of not more than 2.5 MPa, mass flows of a mixture of hydrocarbons of not more than 10 h-1at the same time as the feedstock use of hydrocarbon distillates of different origin with end boiling point not higher than 400°and as a catalyst for use zeolite aluminosilicate composition with a molar ratio of SiO2/Al2O3not more than 450 selected from the range: 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 introduced into the structure at the stage of synthesis of element selected from a number of: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium, characterized in that formed in the reaction products of RA is really in the separator under such conditions, the hydrocarbon, C5remain in the gas phase with gaseous under normal conditions a hydrocarbon, C1-C4obtained mixtureseparated from the gasoline and diesel fuel and served in the second reactor filled with a porous catalyst, in which of these hydrocarbons form a concentrate of aromatic hydrocarbons total aromatic content6-C9not less than 95 wt.%.

2. The method according to claim 1, characterized in that the catalyst in the second reactor, using material from a number of 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 introduced into the structure at the stage of synthesis of elements selected from a number of: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium.

3. The method according to claim 2, characterized in that the catalyst 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 element in an amount of not more than 10 wt.%.

4. The method according to claim 2, characterized in that the catalyst in the second reactor, is prepared by introducing EXT the file by impregnation and/or ion exchange method at a temperature of more than 20° With, 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.

5. The method according to claim 1, characterized in that the conversion of raw materials in the second reactor is carried out at a temperature of 350-600°C, pressure of not more than 2.5 MPa, at a weight flow rate of the gas mixture is not more than 5 h-1.

6. The method of producing gasoline with an octane rating no lower than 83 by the motor method and diesel fuel with a pour point of not higher than -35°consisting in the conversion of hydrocarbons in the presence of porous catalyst at a temperature of 250-500°C, pressure of not more than 2.5 MPa, mass flows of a mixture of hydrocarbons of not more than 10 h-1at the same time as the feedstock use of hydrocarbon distillates of different origin with end boiling point not higher than 400°and as a catalyst for use zeolite aluminosilicate composition with a molar ratio of SiO2/Al2O3not more than 450 selected from the range: 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 introduced into the structure at the stage of synthesis of element selected from a number of: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium,characterized in that that formed during the reaction products are separated in a separator under such conditions that the hydrocarbon, C5remain in the gas phase with gaseous under normal conditions a hydrocarbon, C1-C4obtained mixtureseparated from the gasoline and diesel fuel and served in the second reactor filled with a porous catalyst at the outlet of the second reactor, the products are divided into high-octane gas and liquid, which is mixed with the gasoline fraction separated from the product of the first reactor.

7. The method according to claim 6, characterized in that the catalyst in the second reactor, using material from a number of 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 introduced into the structure at the stage of synthesis of elements selected from a number of: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium.

8. The method according to claim 7, characterized in that the catalyst 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 element in an amount of not more than 10 wt.%.

9. The method according to claim 7, distinguish the different topics the catalyst in the second reactor, is prepared by introducing additives by impregnation and/or ion exchange method at a temperature of more than 20°With, 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.

10. The method according to claim 6, characterized in that the conversion of raw materials in the second reactor is carried out at a temperature of 350-600°C, pressure of not more than 2.5 MPa, at a weight flow rate of the gas mixture is not more than 5 h-1.

11. The method according to claim 6, characterized in that the liquid products of the second reactor is mixed with the gasoline fraction product of the first reactor in the ratio, producing gasoline with the desired octane number.

12. The method of producing gasoline with an octane rating no lower than 83 by the motor method and diesel fuel with a pour point of not higher than -35°consisting in the conversion of hydrocarbons in the presence of porous catalyst at a temperature of 250-500°C, pressure of not more than 2.5 MPa, mass flows of a mixture of hydrocarbons of not more than 10 h-1at the same time as the feedstock use of hydrocarbon distillates of different origin with end boiling point not higher than 400°and as a catalyst for use zeolite aluminosilicate with malamatenios SiO 2/Al2O3not more than 450 selected from the range: 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 introduced into the structure at the stage of synthesis of element selected from a number of: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium, characterized in that before applying in the first reactor from the source of hydrocarbons is distilled off part of straight-run gasoline fraction, which is then sent to the node compounding, the rest of the raw material is transformed into the first reactor, formed during the reaction products are separated in a separator under such conditions that the hydrocarbon, C5remain in the gas phase with gaseous under normal conditions a hydrocarbon, C1-C4obtained mixtureseparated from the gasoline and diesel fuel and served in the second reactor filled with a porous catalyst at the outlet of the second reactor, the products are divided into high-octane gas and liquid which is blended with straight-run gasoline fraction, removed from the source of raw materials.

13. The method according to item 12, wherein as the catalyst in the second reactor, using material from a number of zeolites: ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA with a molar ratio of SiO2/Al2O 3not more than 450, galloylated and haloaluminate, relatoseroticos, zhelezohromovye, hamiliton, hromosomadelita with the structure of ZSM-5 and/or ZSM-11, ZSM-48, BETA introduced into the structure at the stage of synthesis of elements selected from a number of: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium.

14. The method according to item 13, wherein the catalyst 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 element in an amount of not more than 10 wt.%.

15. The method according to item 13, wherein the catalyst in the second reactor, is prepared by introducing additives by impregnation and/or ion exchange method at a temperature of more than 20°With, 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.

16. The method according to item 12, characterized in that the process of turning raw materials in the second reactor is carried out at a temperature of 350-600°C, pressure of not more than 2.5 MPa, at a weight flow rate of the gas mixture is not more than 5 h-1.

17. The method according to item 12, characterized in that the liquid products of the second reactor is mixed with straight-run gasoline fraction in ratios that provide gasoline demand is m-octane.



 

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11 cl, 4 dwg, 3 tbl, 16 ex

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11 cl, 4 dwg, 3 tbl, 16 ex

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