The catalyst for the production of motor fuels (options) and the method of its preparation (options)

 

The described catalysts for the production of gasoline with an octane rating no lower than 83 by the motor method and with a sulfur content in gasoline of less than 0.015% and diesel fuel with a sulfur content of not more than 0.05% of distillate oil or gas condensates with end boiling point not higher than 400°C and with a total content of derivatives of thiophene no more than 40 wt.%, that corresponds to the total sulfur content of 10 wt.%, containing on the surface of 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, or gallosilikata, haloaluminate, gelatoria, zhelezohromovye, rosilicate, hromosomadelita with the structure of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or alumophosphate with the structure of AlPO-5, AlPO-11, AlPO-31, AlPO-41, AlPO-36, AlPO-37, AlPO-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, molybdenum compounds and cobalt and/or Nickel; as compounds of molybdenum and cobalt and/or Nickel is used as at least one bimetallic compound of General formula[MOxO4Ly(H2O)z], where K is a cation Ni2+or Co2+; L is a ligand, Padstow = 2, 3, 4, or 6; z is an integer from 0 to 8, and the concentration of the bimetallic complex compounds in the catalyst is from 1.0 to 25.0 wt.%. The technical result - the production of gasoline with an octane rating no lower than 83 by the motor method and with a sulfur content in gasoline of less than 0.015% and diesel fuel with a sulfur content of not more than 0.05%. 6 c. and 6 C.p. f-crystals, 3 tables.

The invention relates to catalysts for the production of motor fuels and methods for their preparation.

To date, the vast majority of catalytic processes for obtaining high-quality motor fuels from a variety of hydrocarbons based on separate production of gasoline and diesel fuel. A only exceptions are the processes of Hydrotreating and hydrodewaxing of diesel fuel, where as a by-product formed a small amount of gasoline [Pappal D. A., Hilbert, T. L. Isomerisation dewaxing: a new selective process. Petroleum Technology Qarterly, Summer 1996, p. 35-41]. Only a very small number of processes focused on targeted joint production of gasoline and diesel fuel in a reactor and in the presence of the same catalyst. Thus, the known catalysts for one-step high octane gasoline and di is eat the following composition, wt.%: servicecompany zeolite type pentasil with a molar ratio of SiO2/Al2O3=25-160 - 20-70; iron oxide or a mixture of iron oxide and zinc oxide, or a mixture of iron oxide with zinc oxide and/or gallium oxide is 0.05 to 2.5; binder - the rest. This catalyst has a significant drawback, namely it allows to obtain a motor fuel with a relatively small outputs - total not more than 74,3 wt.% gasoline and diesel fuel. In addition, by using this catalyst can be recycled in a motor fuel only light hydrocarbons with the number of carbon atoms is not more than 7, which corresponds to the boiling point of the feedstock is no more than 100C. This limitation restricts the range of raw materials used does not allow to process middle and light distillates most well-known oil and gas condensate fields.

For processing heavier feedstocks other suitable catalyst [RF Application No. 94041731, C 10 G 35/095, 10.10.96]. This catalyst has the following composition, wt.%: - type zeolite with a molar ratio of SiO2/Al2O3equal to from 4.0 to 8.0, - 0,05-5,0, high-silica zeolite with a molar ratio of SiO2/Al2O3equal to from 20 to 100, - Syria, however, it's not removed sulfur-containing compounds, with concentrations in gasoline and diesel fuel is highly regulated by the relevant Standards [GOST R 51866-2002, unleaded Gasoline; GOST 305-82, diesel Fuel].

The closest in technical essence and the achieved effect to the proposed technical solution is the catalytic processing of petroleum distillates [RF Patent №2181750, C 10 G 35/095, 27.04.02]. According to this method for processing oil distillate containing sulfur compounds in quantities not exceeding 10 wt.% in terms of elemental sulfur, using a porous catalyst comprising 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. The second option is known solutions 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 option known solution differs in that the catalyst is lumotast structure type l-5, l-11, l-31, l-41, l-36, l-37, l-40 entered in p, is admi.

In each case the known solution, the zeolite or equivalent component may contain as an additive compound, 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.%. For each variant in the zeolite or equivalent component, the additive is introduced by impregnation and/or ion exchange method at a temperature of 15Or more, 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.

In each case the known solution, the zeolite or equivalent component used in the form of particles ranging in size from 0.05 to 5 mm or balls or extrudates with a diameter of from 0.05 to 5 mm, formed using a binder material, or without it.

Known catalyst used in the conversion of raw materials with a relatively high concentration of sulfur, however, almost without containing compounds thiophene series. Meanwhile, petroleum distillates sulfur is often part of the most chemically stable compounds, thiophene and its homologues, the content of which is 50 m is Novosibirsk: Science. Siberian branch, 1986, S. 5-29; Iris K. N., Mascot E. L., Smirnov, C. K. problems of production of low-sulfur diesel fuels. - Chemistry and technology of fuels and oils, 2003, No. 1-2, S. 21].

In this regard, below, in example 1 the results of the production of motor fuels on a well-known catalyst, is used as raw material oil distillate with the end of the boil 360With a total sulfur content of 5 wt.%, containing 3.8 wt.% thiophene and 2 wt.% dibenzothiophene. The test is carried out in the mode of production of gasoline Regular Euro-92, for which the octane number determined by the motor method (hereinafter everywhere ACM) must be not less than 83, and a sulfur concentration of not more than 150 mg/kg (equivalent to 0, 015 wt.%) [GOST R 51866-2002, unleaded Gasoline]. At a temperature of 350C, a pressure of 10 ATM and the weight flow rate of the raw material 2 h-1in the first 2-3 h get the gasoline complies with GOST R 51866-2002, however, already after 4 h of work OCM get gasoline is reduced to 82, while the residual sulfur content in gasoline exceeds 0.08 wt.%. Such a sharp decline in the quality of gasoline due to rapid deactivation of the catalyst of the prototype under the reaction conditions.

Thus, the main disadvantage of the known ka is uranium thiophene sulfur due to the rapid deactivation of the catalyst.

The present invention solves the problem of creating an improved catalyst for producing high-octane gasoline and diesel fuel from hydrocarbon raw materials with high content of thiophene and its derivatives, characterized in comparison with the catalyst of the prototype high stability of the catalytic activity and, consequently, high octane number of the produced gasoline and low sulphur content in the fuels.

The problem is solved by the fact that as the catalyst for one-step production of gasoline with an octane rating no lower than 83 by the motor method with a sulfur content of less than 0.015 wt.% and diesel fuel with a sulfur content of not more than 0.05 wt.% of hydrocarbons with a total content of derivatives of thiophene no more than 40 wt.% (which corresponds to the total sulfur content of 10 wt.%) use at least one bimetallic compound of the formula[MoxO4Ly(H2O)z], where K is a cation Ni2+or With2+; L is a ligand, representing deprotonirovannoi connection of row: water, mineral acid, carboxylic acid; x=2 or 3; y=2, 3, 4, or 6; z is an integer from 0 to 8; deposited on the zeolite aluminosilicate composition with the second solution different from the first order, as the catalyst used is at least one bimetallic compound of General formula[MoxO4Ly(H2O)z], where K is a cation Ni2+or Co2+; L is a ligand, representing deprotonirovannoi connection of row: water, mineral acid, carboxylic acid; x=2 or 3; y=2, 3, 4, or 6; z is an integer from 0 to 8; instead of zeolite deposited on the 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 is at least one bimetallic compound of General formula[MoxO4Ly(H2O)z], where K is a cation Ni2+or With2+; L is a ligand, representing deprotonirovannoi connection of row: water, mineral acid, carboxylic acid; x=2 or 3; y=2, 3, 4, or 6; z is an integer from 0 to 8; instead of zeolite deposited on 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 a number of: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium.

In each case the solution C is 05 to 5 mm, formed using a binder material, or without it.

For all the above options, there is an optimal concentration of the bimetallic complex compounds in the catalyst, which lies in the range from 1.0 to 25.0 wt.%, the rest of the above zeolites or equivalent materials. When the content in the catalyst is less than 1.0% of the bimetallic complex compounds properties of the catalyst has almost the same stability in the production of gasoline and diesel fuel as the source, not containing caused connection material. The concentration of the applied compounds more to 25.0 wt.% in the catalyst dramatically lowers the octane number of the produced gasoline.

For all these variants, the common method of preparation of the catalyst, which consists in the synthesis solution bimetallic complex compounds of the General formula[MoxO4Ly(H2O)z], where K is a cation Ni2+or With2+; L is a ligand, representing deprotonirovannoi connection of row: water, mineral acid, carboxylic acid; x=2 or 3; y=2, 3, 4, or 6; z is an integer from 0 to 8; and then impregnating the resulting solution of one of the above zeolites or replacement zeolite materialities proposed catalyst in the above three options from well-known is the presence in its structure of at least one bimetallic complex compounds of General formula[MoxO4Ly(H2O)z], where K is a cation Ni2+or With2+; L is a ligand, representing deprotonirovannoi connection of row: water, mineral acid, carboxylic acid; x=2 or 3; y=2, 3, 4, or 6; z is an integer from 0 to 8.

The principal difference of the proposed method of preparation of the catalyst is used for the preparation of the catalyst solution of at least one bimetallic complex compounds of the General formula[MoxO4Ly(H2O)z], where K is a cation Ni2+or With2+; L is a ligand, representing deprotonirovannoi connection of row: water, mineral acid, carboxylic acid; x=2 or 3; y=2, 3, 4, or 6; z is an integer from 0 to 8.

The technical effect of the proposed catalysts and methods for their preparation consists in the fact that the new catalysts, obtained by the claimed method, allow one-stage process into gasoline with an octane rating no lower than 83 by the motor method with a sulfur content of less than 0.015 wt.% and diesel fuel with a sulfur content of not more than 0.05 wt.% various hydrocarbons with a total content of derivatives of thiophene no more than 40 wt.% (which corresponds to the total sulfur content of 10 wt.%). However, Haskovo steps as compared with the known catalysts.

A detailed description of the proposed technical solutions

As starting material for the synthesis of bimetallic complex compounds using one of the compounds of molybdenum General formula Katn[MoxO4Ly(H2O)z] where Kat is at least one cation from the series: N+, NH+4N2N+5; L is a ligand, representing deprotonirovannoi connection of row: water, mineral acid, carboxylic acid; n=1 or 2; x=2 or 3; y=2, 3, 4, or 6; z is an integer from 0 to 8. Typically, the compound contains a spanning fragment [Mo2O4] or [Mo3O4] interatomic distances mo-Mo 2,500,04in which molybdenum has a degree of oxidation, respectively+and 4+. Methods of synthesis of such compounds, their structure and properties, as well as data from NMR, EXAFS, IR, x-ray photoelectronic spectroscopy is described in detail in [Klimov O. C. Synthesis and properties fixed on Al2About3molybdenum-containing catalysts obtained using complexes of various nuclearwaste. Diss. K. H. N., , Novosibirsk, 1994]. Next, the source compound of molybdenum dissolved in the required amount of water>Aiwhere M is a cation of N2+or With2+; D - H2O or NH3; And the anion of a mineral or carboxylic acid; b is 1, 2 or 3; g is an integer from 0 to 6; q is 1 or 2. The concentration and amount of the mixed solutions is determined by either the chemical composition of the resulting bimetallic compounds, or the required concentration of this compound in the catalyst.

During the mixing of solutions of compounds of molybdenum and Nickel and/or cobalt) is formed to the desired connection, the formation of which in solution can be judged by NMR data on nuclei Mo95. Because cobalt and Nickel are paramagnetic, the gradual addition of compounds to the solution of diamagnetic compounds of molybdenum causes a drop in signal intensity of the NMR Mo95proportional to the molar ratio of compounds of cobalt/Nickel and molybdenum. For example, the intensity of the NMR signal Mo95from the original molybdenum compounds after addition of a solution of 0.01 mole of cobalt nitrate Co(NO3)2HN2O to a solution containing 0,02 mol (NH4)2[Mo3O4(C2O4)3(H2O)3] decreases in 2 times. In this case, the solution of one atom of cobalt have Shehadeh molybdenum compounds are completely disappears. This indicates the formation in solution of a bimetallic compound in which the cobalt is relatively close to the molybdenum, and one cobalt atom has three atoms of molybdenum. Obtained in solution the compound can be isolated in solid form and characterized by using elemental analysis, EXAFS and IR spectroscopy. Because we were unable to obtain a sufficiently large crystals, x-ray diffraction analysis was not conducted.

The data of elemental analysis confirm the results of NMR nuclei Mo95. So, in the case of the synthesis of compounds With[Mo3O4(C2O4)3(H2O)3] obtained good agreement between the experimentally defined and calculated (in parentheses) values of concentrations of molybdenum and cobalt, respectively 39,2 (39,5) and 8.0 (8,1) wt.%. For all compounds used (see examples) the difference between the experimentally found and calculated concentrations of molybdenum and cobalt/Nickel did not exceed 5 absolute %.

Data EXAFS spectroscopy, where all received bimetallic complex compounds remained the main interatomic distances, typical starting compounds of molybdenum, indicate identical and/or Nickel in the composition of the resulting connection may take only position, previously occupied by cations of N+, NH+4N2H+5.

The conclusions made on the basis of elemental analysis, NMR and EXAFS spectroscopy in very good agreement with the results of IR spectroscopy. Along with retaining its position as the bands of the parent compounds of molybdenum marked a significant shift of the absorption bands corresponding to the vibrations of the links between atoms of molybdenum and oxygen atoms, most similar to the cobalt and/or Nickel (PL. 1). Therefore, the obtained bimetallic compound has the same structure as the original compounds of molybdenum, with the difference that the cobalt and/or Nickel occupy the position previously occupied by cations of N+, NH+4or N2H+5.

The combination of the obtained results allows to assume that when the contact of the aqueous solutions containing the required for the stoichiometry of the number of one of the compounds of molybdenum General formula Katn[MoxO4Ly(H2O)z] where Kat is at least one cation from the series: N+, NH+4N2H+5; L is a ligand, representing deprotonirovannoi connection of row: water, mineral acid, carb Mb(D)gAiwhere M is a cation Ni2+or With2+D - H2O or NH3; And the anion of a mineral or carboxylic acid; b is 1, 2 or 3; g is an integer from 0 to 6; q is 1 or 2, is formed in the solution bimetallic compound of General formula[MoxO4Ly(H2O)z], where K is a cation Ni2+or With2+; L is a ligand, representing deprotonirovannoi connection of row: water, mineral acid, carboxylic acid; x=2 or 3; y=2, 3, 4, or 6; z is an integer from 0 to 8.

Received bimetallic complex compound by impregnation is applied on at least one of materials selected from the range: 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 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 a number of: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium. The concentration of the impregnating solution podbur,0 to 25.0 wt.% supported bimetallic complex compounds, the rest of the above zeolites or equivalent materials.

The mapping of the data of elemental analysis, IR and EXAFS spectroscopy bimetallic compounds as in its original form and deposited on the surface of zeolites or substitute materials indicates complete identity before and after application.

The examples below are described the present invention, is illustrated implementation, and comparison of the proposed solution with known. Since, as mentioned above, the catalytic activity will change over time, for all catalysts the values of octane number of gasoline determined by the motor method (hereinafter OCM), and the sulfur content in gasoline and diesel fuel products, collected over 10 hours of the process.

Example 1. According to well-known solution powder of zeolite ZSM-5 with a molar ratio of SiO2/Al2O3=60 formed together with 20 wt.% pseudoboehmite lO(HE) as a binder, the sample is dried and calcined by known methods. Forth from it is prepared fraction 0,2-0,8 mm 5 g of the obtained catalyst is placed in a flow reactor, blow air (5 l/h) at a temperature of 500With over 2 is rasaut flow of nitrogen. Then, at this temperature and a pressure of 10 kgf/cm2start the flow of oil distillate NK-360With a total sulfur content of 5 wt.%, containing 3.8 wt.% thiophene and 2 wt.% studied. The mass flow rate of distillate 2,0 h-1. The experiment continued for 10 hours, and then collected in the refrigerator separator liquid products are separated into gasoline (NC-195C) and diesel (195-360(C) fractions. The resulting gasoline has an octane number 76 by the motor method and contains compounds of sulfur in the amount of 0.20 wt.% in terms of elemental sulfur, diesel fuel contains sulfur compounds in the amount of 0.30 wt.% in terms of elemental sulfur.

Example 2. According to the proposed solution of 5.0 g (NH (NH4)2[Mo2O4(C2O4)2(H2O)2] dissolved in 15 ml of water. To the resulting solution was added 10 ml of an aqueous solution containing 2.9 g of Co(NO3)2HN2O. impregnated with This solution of 32.9 g fraction of 0.2-0.8 mm zeolite ZSM-5 with a molar ratio of SiO2/Al2O3=60 are molded together with 20 wt.% pseudoboehmite lO(HE) of example 1. Next, the sample is dried first in a fume hood, then underO4)2(H2O)2], the rest of the zeolite. 5 g of the catalyst placed in the reactor and feel similarly to example 1.

The resulting gasoline has an octane number 84 on the motor method and contains sulfur in a quantity of 0.005 wt.% in terms of elemental sulfur, diesel fuel contains sulfur in a quantity of 0.02 wt.% in terms of elemental sulfur.

Examples 3-22, illustrating the influence of nature and concentration of supported bimetallic complex compounds, the nature of the zeolite or equivalent material properties of the obtained catalysts are shown in table 2.

Examples 23-30, illustrating the influence of particle size of the catalyst and the presence of a binder material therein at the quality of motor fuels, are shown in table 3.

In examples 31-35 described catalysts prepared by deposition of more than one complex bimetallic compounds on the surface of the zeolite or equivalent material.

Example 31. 5.0 g (NH4)2[Mo2O4(C2O4)2(H2O)2] dissolved in 15 ml of water. To the resulting solution was added 10 ml of an aqueous solution containing 2.9 g With[NO3]2HN2O). Is formed in the solution 5,23 g b>2] is denoted as solution 1. The second portion of 5.0 g (NH4)2[Mo2O4(C2O4)2(H2O)2] dissolved in 15 ml of water. To the resulting solution was added 10 ml of an aqueous solution containing 2.9 g of Ni(NO3)2HN2O. is formed In the solution 5,23 g bimetallic complex compounds of the formula Ni[Mo2O4(C2O4)2(H2O)2] is denoted as solution 2. Solutions 1 and 2 are mixed and impregnated with a mixture of 65.8 g fraction of 0.2-0.8 mm zeolite ZSM-5 with a molar ratio of SiO2/Al2O3=60, formed together with 20 wt.% pseudoboehmite AlO(OH) from examples 1 and 2. The resulting catalyst is dried and feel similar to examples 1 and 2. The catalyst contains 13,72 wt.% total connection With[Mo2O4(C2O4)2(H2O)2] and (NH4)2[Mo2O4(C2O4)2(H2O)2] (6,86 wt.% each).

The resulting gasoline has an octane number 84 on the motor method and contains sulfur in a quantity of 0.005 wt.% in terms of elemental sulfur, diesel fuel contains sulfur in a quantity of 0.02 wt.% in terms of elemental sulfur.

Example 32. 5.0 g (NH4)2[Mo2O43)2HN2O and 1.45 g of Ni(NO3)2HN2A. forming a solution containing 2,615 wt.% With[Mo2O4(C2O4)2(H2O)2] and (NH4)2[Mo2O4(C2O4)2(H2O)2]. This impregnate solution of 32.9 g fraction of 0.2-0.8 mm zeolite ZSM-5 with a molar ratio of SiO2/Al2O3=60, formed together with 20 wt.% pseudoboehmite lO(HE) of example 1. Further, similar to examples 1 and 2.

The resulting gasoline has an octane number of 85 by the motor method and contains compounds of sulfur in the amount of 0.007 wt.% in terms of elemental sulfur, diesel fuel contains sulfur in a quantity 0.017 wt.% in terms of elemental sulfur.

Example 33. 5.0 g (NH4)2[Mo2O4(C2O4)2(H2O)2] dissolved in 15 ml of water. To the resulting solution was added 10 ml of an aqueous solution containing of 2.45 g of Co(NO3)2HN2O and 0.45 g of Ni(NO3)2x6H2A. forming a solution containing 4,42 wt.% With[Mo2O4(C2O4)2(H2O)2] and 0.81 wt.% (NH4)2[Mo2O4(C2O4)2(H2O)2]. Then all the analogues is the number of 0.01 wt.% in terms of elemental sulfur, diesel fuel contains sulfur in a quantity is 0.023 wt.% in terms of elemental sulfur.

Example 34. 5,0 (NH4)2[Mo3O4(C2O4)3(H2O)3] And 5.0 g (NH4)2[Mo2O4(C2O4)2(H2O)2] dissolved in 30 ml of water. To the resulting solution was added 20 ml of an aqueous solution containing 5.8 g of Co(NO3)2HN2A. forming a solution containing 5,23 g With[Mo2O4(C2O4)2(H2O)2] 5,16 g With[Mo3O4(C2O4)3(H2O)3]. The resulting solution is impregnated with 65,8 g fraction of 0.2-0.8 mm zeolite ZSM-5 is similar to example 31. The resulting catalyst is dried and feel similar to examples 1 and 2. The catalyst contains 13,63 wt.% total connection With[Mo2O4(C2O4)2(H2O)2] and With[Mo3O4(C2O4)3(H2O)3] (6,86 wt.% first and 6,77 wt.% the second).

The resulting gasoline has an octane number of 85 by the motor method and contains sulfur in a quantity 0,009 wt.% in terms of elemental sulfur, diesel fuel contains sulfur compounds in amounts of 0.025 wt.% in terms of elemental sulfur.

P is ub>2[Mo2O4(C2O4)2(H2O)2] dissolved in 30 ml of water. To the resulting solution was added 20 ml of an aqueous solution containing 5.8 g of Co(NO3)2HN2A. forming a solution containing 5,23 g With[Mo2O4(C2O4)2(H2O)2] 5,16 g With[Mo3O4(C2O4)3(H2O)3] - denote the solution 1. 5.0 g (NH4)2[Mo2O4(C2O4)2(H2O)2] dissolved in 15 ml of water. To the resulting solution was added 10 ml of an aqueous solution containing 2.9 g of Ni(NO3)2HN2O get a solution 2 containing 5,23 g bimetallic complex compounds of the formula Ni[Mo2O4(C2O4)2(H2O)2]. Solutions 1 and 2 are mixed, the mixture is impregnated with 65,8 g fraction of 0.2-0.8 mm zeolite ZSM-5 is similar to example 31. After drying, the catalyst contains 6.42 per wt.% With[Mo2O4(C2O4)2(H2O)2], 6.42 per wt.% Ni[Mo2O4(C2O4)2(H2O)2] and to 6.43 wt.% With[Mo3O4(C2O4)3(H2O)3] total MT 19: 18 wt.% bimetallic complex compounds.

The resulting gasoline has an octane Zelenoe fuel contains sulfur in a quantity at 0.020 wt.% in terms of elemental sulfur.

Thus, as seen from the above examples and tables, the proposed variants of the catalyst prepared on the proposed variants of the method, allows to obtain in a single reactor in a single phase gasoline with an octane rating no lower than 83 by the motor method and with a sulfur content in gasoline of less than 0.015% and diesel fuel with a sulfur content of not more than 0.05% of hydrocarbons with a high content of thiophene and its derivatives.

Claims

1. The catalyst for producing gasoline with an octane rating no lower than 83 by the motor method and with a sulfur content in gasoline of less than 0.015% and diesel fuel with a sulfur content of not more than 0.05% of distillate oil or gas condensates with end boiling point not higher than 400°C and with a total content of derivatives of thiophene no more than 40 wt.%, that corresponds to the total sulfur content of 10 wt.%, containing on the surface of 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, compounds of molybdenum and cobalt and/or Nickel, characterized in that compounds of molybdenum and cobalt and/or Nickel is used as at least one bimetallic complex joint is the ligand, representing deprotonirovannoi connection of a number of water, mineral acid, carboxylic acid;

x = 2 or 3;

y = 2, 3, 4, or 6;

z is an integer from 0 to 8,

the concentration of the bimetallic complex compounds in the catalyst is from 1.0 to 25.0 wt.%.

2. The catalyst p. 1, characterized in that it represents a particle size of from 0.05 to 5 mm, or pellets, or extrudates with a diameter of from 0.05 to 5 mm, formed using a binder material, or without it.

3. The method of preparation of a catalyst to produce gasoline with an octane rating no lower than 83 by the motor method and with a sulfur content in gasoline of less than 0.015% and diesel fuel with a sulfur content of not more than 0.05% of distillate oil or gas condensates with end boiling point not higher than 400°C and with a total content of derivatives of thiophene no more than 40 wt.%, that corresponds to the total sulfur content of 10 wt.%, includes impregnation of 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, aqueous solution of compounds of molybdenum and cobalt and/or Nickel, followed by drying in air or in an inert gas atmosphere, characterized in that compounds of molybdenum and sub>xO4Ly(H2O)z],

where K is a cation Ni2+or With2+;

L is a ligand, representing deprotonirovannoi connection of a number of water, mineral acid, carboxylic acid;

x = 2 or 3;

y = 2, 3, 4, or 6;

z is an integer from 0 to 8.

4. The method according to p. 3, characterized in that the aqueous solution of the original bi-metal complex compounds has a concentration that impregnation on the capacity of 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, provides a total content of from 1.0 to 25.0 wt.% bimetallic complex compounds in the dried catalyst, the zeolite is a particle size of from 0.05 to 5 mm, or pellets, or extrudates with a diameter of from 0.05 to 5 mm, formed using a binder material, or without it.

5. The catalyst for producing gasoline with an octane rating no lower than 83 by the motor method and with a sulfur content in gasoline of less than 0.015% and diesel fuel with a sulfur content of not more than 0.05% of distillate oil or gas condensates with end boiling point not higher than 400°C and with a total content of derivatives of thiophene no more than 40 wt.%, what is relevant is the aluminosilicate, gelatoria, telesolutions, prosilica, chromalusion with the structure of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, compounds of molybdenum and cobalt and/or Nickel, characterized in that compounds of molybdenum and cobalt and/or Nickel is used as at least one bimetallic compound of General formula

To[MoxO4Ly(H2O)z],

where K is a cation Ni2+or With2+;

L is a ligand, representing deprotonirovannoi connection of a number of water, mineral acid, carboxylic acid;

x = 2 or 3;

y = 2, 3, 4, or 6;

z is an integer from 0 to 8,

the concentration of the bimetallic complex compounds in the catalyst is from 1.0 to 25.0 wt.%.

6. The catalyst p. 5, characterized in that it represents a particle size of from 0.05 to 5 mm, or pellets, or extrudates with a diameter of from 0.05 to 5 mm, formed using a binder material, or without it.

7. The method of preparation of a catalyst to produce gasoline with an octane rating no lower than 83 by the motor method and with a sulfur content in gasoline of less than 0.015% and diesel fuel with a sulfur content of not more than 0.05% of distillate oil or gas condensates with end boiling point not higher than 400°C and with a total content of thiophene derivatives of the series gallosilikata, haloaluminate, gelatoria, telesolutions, prosilica, chromalusion with the structure of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, aqueous solution of compounds of molybdenum and cobalt and/or Nickel, followed by drying in air or in an inert gas atmosphere, characterized in that compounds of molybdenum and cobalt and/or Nickel is used as at least one bimetallic compound of General formula

To[MoxO4Ly(H2O)z],

where K is a cation Ni2+or With2+;

L is a ligand, representing deprotonirovannoi connection of a number of water, mineral acid, carboxylic acid;

x = 2 or 3;

y = 2, 3, 4, or 6;

z is an integer from 0 to 8.

8. The method according to p. 7, characterized in that the aqueous solution of the original bi-metal complex compounds has a concentration that impregnation on the capacity of a material selected from a range gallosilikata, haloaluminate, gelatoria, telesolutions, prosilica, chromalusion with the structure of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, provides a total content of from 1.0 to 25.0 wt.% bimetallic complex compounds in the dried catalyst, the source material is a particle size of from 0.05 to 5 mm, or is acting

9. The catalyst for producing gasoline with an octane rating no lower than 83 by the motor method and with a sulfur content in gasoline of less than 0.015% and diesel fuel with a sulfur content of not more than 0.05% of distillate oil or gas condensates with end boiling point not higher than 400°C and with a total content of derivatives of thiophene no more than 40 wt.%, that corresponds to the total sulfur content of 10 wt.%, containing on the surface of a material selected from a range 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 a number of magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium, molybdenum compounds and cobalt and/or Nickel, characterized in that as compounds of molybdenum and cobalt and/or Nickel is used as at least one bimetallic compound of General formula

To[MoxO4Ly(H2O)z],

where K is a cation Ni2+or Co2+;

L is a ligand, representing deprotonirovannoi connection of a number of water, mineral acid, carboxylic acid;

x = 2 or 3;

y = 2, 3, 4, or 6;

z is an integer from 0 to 8,

the concentration of the bimetallic complex compounds in the catalyst is from 1.0 to 25.0 wt.%.

10. Caduti diameter of from 0.05 to 5 mm, formed using a binder material, or without it.

11. The method of preparation of a catalyst to produce gasoline with an octane rating no lower than 83 by the motor method and with a sulfur content in gasoline of less than 0.015% and diesel fuel with a sulfur content of not more than 0.05% of distillate oil or gas condensates with end boiling point not higher than 400°C and with a total content of derivatives of thiophene no more than 40 wt.%, that corresponds to the total sulfur content of 10 wt.%, including impregnation material selected from a number of 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 a number of magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium, aqueous solution of compounds of molybdenum and cobalt and/or Nickel, followed by drying in air or in an inert gas atmosphere, characterized in that as compounds of molybdenum and cobalt and/or Nickel is used as at least one bimetallic compound of General formula

To[MoxO4Ly(H2O)z],

where K is a cation Ni2+or With2+;

L is a ligand, representing deprotonirovannoi connection of a number of water, mineral acid, carboy solution of the original bi-metal complex compounds is the concentration, which when impregnated on the capacity of a material selected from a range 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 a number of magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium, provides a total content of from 1.0 to 25.0 wt.% bimetallic complex compounds in the dried catalyst, the source material is a particle size of from 0.05 to 5 mm, or pellets, or extrudates with a diameter of from 0.05 to 5 mm, formed using a binder material or without him.

 

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