RU2557248C2 - Catalyst, method of thereof preparation and process of selective hydrodesulphurisation of olefin-containing hydrocarbon raw material - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to catalyst of selective hydrodesulphurisation of olefin-containing hydrocarbon raw material. Said catalyst consists of compounds of metals Co or Ni, Mo and Na or K, applied on carrier. Claimed catalyst contains bimetal complex compound of metals Co or Ni, Mo and Na or K, carboxylic acid, containing, at least, one carboxyl group and 1-20 carbon atoms; it has specific surface 180-350 m²/g, volume of pores 0.3-1.1 cm³/g, average pore diameter 5.5-11.0 nm. Invention relates to method of preparing claimed catalyst, as well as to process of selective hydrodesulphurisation with its application.

EFFECT: claimed catalyst makes it possible to obtain petrol with ultralow content of sulphur and preservation of value of its octane number at initial level.

14 cl, 3 tbl, 9 ex

Description

The invention relates to the field of chemistry, in particular to catalysts for the selective hydrodesulfurization of olefin-containing hydrocarbon feedstocks, and can be used in the oil refining and petrochemical industries.

One of the most important tasks of the oil refining industry of the Russian Federation is to increase the depth of oil refining. This is possible only with an increase in the share of deep processing processes (catalytic cracking, hydrocracking, coking, thermal cracking) in the structure of oil refineries. Against the background of a constant deterioration in the quality of oils (weighting, a decrease in the content of fractions boiling up to 350 ° C, an increase in the concentration of heteroatomic compounds, etc.), environmental requirements for motor fuels are being tightened. The expected increase in the fleet of cars in Russia by 2015 (almost 1.5 times), mainly due to cars that comply with environmental class 4, now requires preparation for the production of gasolines that meet the requirements of class 4 and 5 of the technical regulation.

In modern gasolines, the content of aromatic hydrocarbons (including benzene), sulfur and unsaturated compounds is limited. The most stringent requirements are related to the total sulfur content in motor fuels. So, for motor gasoline, according to the technical regulation, the sulfur content is limited to less than 150 ppm (class 3), 50 ppm (class 4) and 10 ppm (class 5). The chemical composition requirements also change the existing gasoline production scheme: the proportion of reformate is reduced, the proportions of catalytic cracking gasoline, isomerizate and alkylate are increasing. Given the relatively low productivity of catalytic isomerization and alkylation units, the main burden on the formation of a gasoline fund remains with catalytic cracking gasoline, but even in modern plants (such as FCC), it is not possible to obtain a component of gasoline classes 4 and 5, since high-octane catalytic cracking gasolines are sources of 90% sulfur when compounding commercial fuels.

To reduce the sulfur content in catalytic cracking gasolines, two methods are used - preliminary hydrotreating of catalytic cracking unit feedstock and catalytic cracking gasoline hydrotreating. It is difficult to solve the problem by preliminary hydrotreating the catalytic cracking feedstock, since ultra-deep purification of vacuum gas oil (up to a total sulfur content of less than 200 ppm) from hard-to-remove sterically shielded organosulfur compounds is necessary. Hydrotreating of catalytic cracking gasoline (the second method) on standard Al-Ni (Co) -Mo (W) catalysts does not proceed selectively, along with hydrodesulfurization reactions, deep hydrogenation of olefinic hydrocarbons occurs, which reduces the octane number of the purified gasoline component.

The development of modern catalysts for the selective hydrogenolysis of sulfur-containing compounds of olefin-containing hydrocarbon feedstocks is the most effective solution to this problem.

To create catalysts for the selective hydrotreating of catalytic cracking gasolines and olefin-containing feedstocks, methods are used to form the active component on the surface of a carrier that is optimal in texture and properties due to the following approaches:

1. The use in the composition of the carriers and / or catalysts of alkali and alkaline earth metals that suppress the hydrogenating function of the catalysts (US 5348928, B01J 21/04, B01J 23/78, B01J 23/88, B01J 37/04, 09/20/1994; US 5340466, C10G 45/60, C10G 45/08, 08/23/1994; US 5846406, C10G 45/04, 12/08/1998; US 5358633, C10G 45/08, 10/25/1994, US 5770046, C10G 45/04, 23.06. 1998, US 5525211, C10G 45/08, B01J 23/24, 06/11/1996; US 5851382, C10G 45/04, 12/22/1998). The disadvantage of such catalysts is the low concentration of available active centers, which does not allow deep reactions to hydrodesulfurization to obtain a component of marketable gasoline with an ultra-low sulfur content.

2. The use of organic modifiers that increase the degree of sulfidation of the supported active precursor and selectivity in hydrodesulfurization reactions with respect to olefin hydrogenation reactions (US 8236723, B01J 31/34, B01J 21/08, C10G 45/08, 08/07/2012; WO 2007 / 084438 A2, B01J 23/882, C10G 45/08, 07/26/2007; WO 2007/084439 A1, C10G 45/08, B01J 23/882, B01J 21/08, B01J 35/10, 07/26/2007). The disadvantage of the synthesis of such catalysts is the presence of hydrogenation centers on the surface of the active phase, which does not allow selective hydrotreating of olefin-containing hydrocarbon feeds, especially when producing hydrogenated with a sulfur content of less than 50 ppm.

A common disadvantage for the above catalysts is the low selectivity with respect to olefin hydrogenation reactions at a high hydrodesulfurization depth, and as a result, the octane number is reduced to 5 p. Compared to the original gasoline. The technical solution of the present invention is the creation of a highly dispersed active phase with a high proportion of active centers through the use of a bimetallic complex and an organic modifier, as well as the suppression of hydrogenation centers through the use of metal of the I-A group. The method of preparation of the catalyst by impregnation with a joint solution of all elements allows for the molecular contact of the precursors necessary for the formation of the active phase of the optimal composition and morphology for the selective hydrotreating of olefin-containing hydrocarbon feedstocks.

Closest to the proposed solution is a selective hydrotreatment catalyst and a method for its preparation described in US patent 5348928, B01J 21/04, B01J 23/78, B01J 23/88, B01J 37/04, 09/20/1994. The catalyst includes a hydrogenating component - metals from groups VIB and VIII of the Periodic table with a content of 4-20% wt. and 0.5-10% wt. in terms of oxides, respectively. The catalyst carrier includes magnesium in an amount of 0.5-50% wt. in terms of oxide, alkali metal in an amount of 0.02-10% wt.

A method for preparing a selective catalytic cracking gasoline hydrotreating catalyst comprises the following operations: preparing a first aqueous solution containing dissolved compounds of metals of groups VIB and VIII; mixing the first solution with an inorganic oxide and forming a paste comprising metals of groups VIB and VIII; the transformation of the paste into a composite of at least one of the forms listed from the series: ball, powder, tablets, extrudates; the preparation of a second aqueous solution comprising dissolved compounds of magnesium and an alkali metal; mixing the second aqueous solution with the composite and obtaining an impregnated composite; calcining the resulting composite to obtain a selective hydrotreating catalyst.

The disadvantage of this method of preparation of the catalyst is that metal precursors from groups VIB and VIII of the Periodic table are used, which do not allow the formation of a highly dispersed active phase with a high content of active centers. As a result, firstly, the degree of hydrodesulfurization of olefin-containing raw materials is not reached above 95.5%, and secondly, when the degree of hydrodesulfurization of 80% and higher, the olefin hydrocarbons are hydrogenated to 65%, i.e. the selectivity of the process and, as a consequence, the octane number of the resulting gasoline are reduced. Thus, the catalytic properties of the prototype catalyst do not allow the production of gasoline with an ultra low sulfur content, while maintaining the content of olefinic hydrocarbons and octane values.

The technical result of the present invention is the creation of a new catalyst, a preparation method and a process for the selective hydrodesulfurization of olefin-containing hydrocarbon feedstocks. The technical result is achieved through a catalyst for the selective hydrodesulfurization of an olefin-containing hydrocarbon feed consisting of metal compounds Co or Ni, Mo and Na or K supported on a carrier. The catalyst contains a bimetallic complex compound of metals Co or Ni, Mo and Na or K, a carboxylic acid containing at least one carboxyl group and 1-20 carbon atoms; the catalyst has a specific surface area of 180-350 m ² / g, a pore volume of 0.3-1.1 cm ³ / g, an average pore diameter of 5.5-11.0 nm. As the carrier, alumina, silica or compositions thereof are used. The bimetallic complex compound contains at least one of the following heteropolyanions [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [Co (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [P ₂ Mo ₅ O ₂₃ ] ^6- , [SiMo ₁₂ O ₄₀ ] ^4- , [PMo ₁₂ O ₄₀ ] ^3- , while the content is calcined at 550 ° С the catalyst MoO ₃ is 14.0-23.0% wt, CoO or NiO - 4.0-6.5% wt. potassium oxide (sodium) - 5-10% wt. The catalyst is in the form of cylinders or trefoils.

A method of preparing a catalyst for selective hydrodesulfurization of an olefin-containing hydrocarbon feedstock by impregnating the carrier in terms of moisture capacity or with an excess of a solution of the active component precursors consists in that the carrier is once impregnated with an aqueous solution having a pH of 2.5-4.0 containing at least one of the heteropolyanions of the [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [Co (OH) ₆ Mo ₆ O ₁₈ ] ^4- , Ni (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [P ₂ Mo ₅ O ₂₃ ] ^6- , [SiMo ₁₂ O ₄₀ ] ^4- , [PMo ₁₂ O ₄₀ ] ^3- , one of the cobalt hydroxide series Co (OH) ₂ · nH ₂ O, ( n = 0.5-5) co alt carbonate CoCO _3, basic cobalt carbonate 2CoCO ₃ · 3Co (OH) ₂ · nH ₂ O, (n = 0,5-5) as a Group IA metal compound is used any of a number of potassium hydroxide KOH, potassium carbonate, K ₂ CO ₃ , sodium hydroxide NaOH, sodium carbonate Na ₂ CoO ₃ , a carboxylic acid containing at least one carboxyl group and 1-20 carbon atoms is used as a stabilizer for the impregnating solution.

The method of preparation of the catalyst is that the heteropolyanion [P ₂ Mo ₅ O ₂₃ ] ^6- or [PMo ₁₂ O ₄₀ ] ^3- is formed by sequentially dissolving the molybdenum oxide MoO ₃ or molybdenum acid H ₂ MoO ₄ in 85% phosphoric acid H ₃ PO ₄ and adding a 30% solution of H ₂ O ₂ at a temperature of 50-90 ° C and a pH of 1.0-1.5 in ratios corresponding to stoichiometry in the heteropolyanion. One of the heteropolyanions [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [Co (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- is formed by sequentially dissolving the molybdenum oxide MoO ₃ or molybdenum acid H ₂ MoO ₄ in a 30% hydrogen peroxide solution at a temperature of 50-90 ° C, followed by the addition of a Co or Ni salt in ratios corresponding to stoichiometry in heteropolyanion. For the preparation of the catalyst, citric acid is used as a stabilizer, either the impregnation of the carrier by moisture capacity or from excess solution is used, the granules of the carrier are impregnated after creating a vacuum in a vessel containing the carrier, or after creating a vacuum, it is carried out by impregnating solution at temperatures of 20-50 ° C. After impregnation, the catalyst is dried at a temperature of 120-180 ° C in a stream of air or nitrogen.

A process for the selective hydrodesulfurization of an olefin-containing hydrocarbon feed, which comprises passing an olefin-containing hydrocarbon feed through a layer of the inventive catalyst. The process is carried out at a temperature of 220-320 ° C, a pressure of 0.5-3.0 MPa, a volumetric flow rate of raw materials of 4-12 h ^-1 , a volumetric ratio of hydrogen / raw material of 50-300 m ³ / m ³ .

The starting compounds for the preparation of a joint impregnation solution, the composition and texture characteristics of the carriers used are given in table. one.

The invention is illustrated by the following examples.

Example 1

The composition of the catalyst and the method of its preparation according to the well-known technical solution - the prototype.

The catalyst is prepared by impregnating 100 g of aluminum oxide with a solution of 3.9 g of cobalt nitrate Co (NO ₃ ) ₂ · 6H ₂ O, 7.4 g of ammonium molybdate in 58.7 water. The obtained samples were dried at room temperature, then at 121 ° C for 12 hours, and calcined at 538 ° C for 2 hours. Then, the obtained sample (100 g) was soaked with 6.37 g of Mg (NO ₃ ) ₂ · 6H ₂ O in 58.7 g water. Again, drying was carried out at room temperature, then at 121 ° C for 12 hours, and calcined at 538 ° C for 2 hours.

After calcining in air for 2 hours at 550 ° C, the catalyst contains 5.5% wt. MoO ₃ , 1.0% wt. CoO, 0.9% MgO, 0.3% Na ₂ O (Table 1).

Example 2

To prepare an impregnating solution, 37.6 g of decamolybdicobaltic heteropoly acid H ₆ [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] and 11.9 g of cobalt carbonate CoCO ₃ · nH ₂ O are dissolved in 65 cm ^{3 of} water at 40-60 ° C with stirring. After the evolution of CO _{2 has been completed} , 23.4 g of citric acid monohydrate C ₆ H ₈ O ₇ · H ₂ O and 23.4 g of sodium carbonate Na ₂ CO ₃ · H ₂ O are added to the resulting solution, stirred until the evolution of CO ₂ ceases and the mixture is adjusted volume of water up to 92 cm ³ . The pH of the impregnation solution is 3.0-4.0.

The carrier is alumina modified with SiO ₂ 10% wt. - weighing 100 g is kept in vacuum for 30 minutes, then fill in with an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 8 hours

After calcining in air for 2 hours at 550 ° C, the catalyst contains 21.0% wt. MoO ₃ , 5.5% wt. CoO and 7.7% wt. Na ₂ O (Table 1).

Example 3

To prepare an impregnating solution, 26.4 g of hexamolybdocobalt heteropoly acid H ₄ [Co (OH) ₆ Mo ₆ O ₁₈ ] and 7.9 g of cobalt carbonate CoCO ₃ · nH ₂ O are dissolved in 65 cm ^{3 of} water at 40-60 ° C with stirring . After the completion of the CO ₂ emission, 15.4 g of citric acid monohydrate C ₆ H ₈ O ₇ · H ₂ O and 15.0 g of potassium carbonate K ₂ CO ₃ are added to the resulting solution, stirred until the evolution of CO ₂ ceases and the volume is adjusted with water to 81 cm ³ . The pH of the impregnation solution is 3.0-4.0.

The carrier is alumina modified with SiO ₂ 5% wt. - weighing 100 g is kept in vacuum for 30 minutes, then fill in with an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 8 hours

After calcination in air for 2 hours at 550 ° C, the catalyst contains 16.1% wt. MoO ₃ , 4.0% wt. CoO and 7.4% wt. K ₂ O (table. 1).

Example 4

To prepare an impregnating solution, 27.3 g of hexamolybdon-nickel heteropoly acid H ₄ [Ni (OH) ₆ Mo ₆ O ₁₈ ] and 8.5 g of nickel hydroxocarbonate NiCO ₃ · nNi (OH) ₂ · mH ₂ O are dissolved in 65 cm ^{3 of} water at 40 -60 ° C and with stirring. After the completion of the CO ₂ evolution, 16.7 g of citric acid monohydrate C ₆ H ₈ O ₇ · H ₂ O and 14.7 g of potassium carbonate K ₂ CO ₃ are added to the resulting solution, stirred until the evolution of CO ₂ ceases and the volume is adjusted to 81 with water cm ³ . The pH of the impregnation solution is 3.0-4.0.

The carrier is alumina modified with SiO ₂ 5% wt. - weighing 100 g is kept in vacuum for 30 minutes, then fill in with an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 8 hours

After calcination in air for 2 hours at 550 ° C, the catalyst contains 16.5% wt. MoO ₃ , 4.3% wt. CoO and 7.2% wt. K ₂ O (table. 1).

Example 5

To prepare an impregnating solution, 22.2 g of molybdenum oxide is dissolved in 70 cm ^{3 of} water with the addition of 4.0 g of an 85% phosphoric acid solution at a temperature of 60-90 ° C. Then, 8.2 g of cobalt bicarbonate CoCO ₃ · nCo (OH) ₂ · mH ₂ O, 16.0 g of citric acid monohydrate C ₆ H ₈ O ₇ · H ₂ O and 12.4 g of potassium carbonate K ₂ are added to the resulting solution CO ₃ . After the completion of CO ₂ evolution, the volume of the resulting solution was adjusted with water to 83 cm ³ . The pH of the impregnation solution is 3.0-4.0.

The carrier is alumina modified with SiO ₂ 5% wt. - weighing 100 g is kept in vacuum for 30 minutes, then fill in with an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 8 hours

After calcining in air for 2 hours at 550 ° C, the catalyst contains 16.3% wt. MoO ₃ , 4.2% wt. CoO and 6.2% wt. K ₂ O (table. 1).

Example 6

To prepare an impregnating solution, 34.2 g of cobalt salt of pentamolybdodiphosphoric acid Co ₃ [P ₂ Mo ₅ O ₂₃ ] is dissolved in 70 cm ^{3 of} water, then 16.6 g of citric acid C ₆ H ₈ O ₇ and 11.2 g of potassium carbonate are added. K ₂ CO ₃ . Next, the volume of the resulting solution was adjusted with water to 83 cm ³ . The pH of the impregnating solution is 2.5-3.5.

The carrier is alumina modified with SiO ₂ 5% wt. - weighing 100 g is kept in vacuum for 30 minutes, then fill in with an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 8 hours

After calcining in air for 2 hours at 550 ° C, the catalyst contains 16.4% wt. MoO ₃ , 4.3% wt. CoO and 6.8% wt. K ₂ O (table. 1).

Example 7

To prepare an impregnating solution, 36.5 g of dodecamolybdophosphoric acid H ₃ [PMo ₁₂ O ₄₀ ] is dissolved in 60 cm ^{3 of} water with the addition of 10.7 g of cobalt bicarbonate CoCO ₃ · nCo (OH) ₂ · mH ₂ O and 21.1 g of citric acid acids C ₆ H ₈ O ₇ . After the completion of the CO ₂ evolution, 16.1 g of potassium carbonate K ₂ CO ₃ are added to the resulting solution. After the completion of CO ₂ evolution, the volume of the resulting solution was adjusted with water to 83 cm ³ . The pH of the impregnation solution is 3.0-4.0.

The carrier is alumina modified with SiO ₂ 5% wt. - weighing 100 g is kept in vacuum for 30 minutes, then fill in with an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 8 hours

After calcining in air for 2 hours at 550 ° C, the catalyst contains 19.5% wt. MoO ₃ , 5.0% wt. CoO and 9.0% wt. K ₂ O (table. 1).

Example 8

To prepare an impregnating solution, 35.7 g of dodecamolybdophosphoric acid H ₃ [PMo ₁₂ O ₄₀ ] is dissolved in 80 cm ^{3 of} water with the addition of 10.5 g of cobalt bicarbonate CoCO ₃ · nCo (OH) ₂ · mH ₂ O and 20.6 g of citric acids C ₆ H ₈ O ₇ . After completion of the CO ₂ evolution, 16.5 g of potassium carbonate K ₂ CO ₃ are added to the resulting solution. After the completion of the CO ₂ emission, the volume of the resulting solution was adjusted with water to 136 cm ³ . The pH of the impregnation solution is 3.0-4.0.

Carrier silica gel SiO ₂ weighing 100 g is kept in vacuum for 30 minutes, then pour in an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 8 hours

After calcining in air for 2 hours at 550 ° C, the catalyst contains 19.5% wt. MoO ₃ , 5.0% wt. CoO and 7.6% wt. K ₂ O (table. 1).

Example 9

To prepare an impregnating solution, 32.8 g of dodecamolybdosilicic acid H ₄ [SiMo ₁₂ O ₄₀ ] is dissolved in 80 cm ^{3 of} water with the addition of 11.0 g of cobalt bicarbonate CoCO ₃ · nCo (OH) ₂ · mH ₂ O and 15.3 g of tartaric acids C ₄ H ₆ O ₆ . After completion of the CO ₂ evolution, 15.9 g of potassium carbonate K ₂ CO ₃ are added to the resulting solution. After the completion of CO ₂ evolution, the volume of the resulting solution was adjusted with water to 83 cm ³ . The pH of the impregnation solution is 3.0-4.0.

The carrier is alumina modified with SiO ₂ 5% wt. - weighing 100 g is kept in vacuum for 30 minutes, then fill in with an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 8 hours

After calcining in air for 2 hours at 550 ° C, the catalyst contains 19.5% wt. MoO ₃ , 5.1% wt. CoO and 8.9% wt. K ₂ O (table. 1).

The catalysts were tested in the form of particles 0.25-0.50 mm in size, prepared by grinding and dispersing the initial catalyst granules. The catalytic properties were determined in a laboratory flow-through installation with a micro-reactor during the hydrotreatment of a model mixture consisting of thiophene, n-hexene-1 and n-heptane. The content of sulfur in the raw material is ~ 1000 ppm, n-hexene-1 35.6% wt. The reactor was loaded with a catalyst in an amount of 0.3000 ± 0.0005 g (0.25-0.50 mm fraction) diluted with SiC to a total volume of 1 cm ³ . Process conditions: temperature 220 ° C, pressure 1.5 MPa, H ₂ circulation rate / feed 100 nl / l, OSPS 5 h ^-1 .

Every hour, catalysis was carried out to analyze its composition on a Crystal-5000 gas chromatograph. The reaction products were separated on an OV-101 grafted quartz capillary column.

The selectivity of the catalysts with respect to desulfurization reactions was evaluated by the selective factor calculated by the formula:

$$\mathrm{FROM}.f.GD\mathrm{FROM}=\frac{\ln (\mathrm{one}-x_{t\mathrm{and}\mathrm{about}fen})}{\ln (\mathrm{one}-x_{n-ge\mathrm{to}\mathrm{from}en-\mathrm{one}})},(\mathrm{one})$$

where x _thiophene - _thiophene conversion,%

x _hexene-1 - conversion of n-hexene-1,%.

The results of catalytic tests are presented in table. 2.

table 2 Properties of catalysts in hydrotreating of thiophene-n-hexene-1 feedstock Catalyst number The conversion of thiophene,% The conversion of n-hexene-1,% Selective factor one 12.9 10.3 1.27 2 39.4 17.4 2.62 3 21.2 12.2 1.83 four 29.3 17.4 1.81 5 18.3 10.0 1.92 6 20.7 11.2 1.95 7 34.1 10.3 3.84 8 36.7 13.8 3.08 9 34.3 10.9 3.64

The catalysts obtained by the claimed method show a higher catalytic activity and selectivity. For sample 7, the selective factor is 3.84, which is almost 3 times higher than that of the prototype.

The catalysts were tested during the hydrotreating of gasoline fractions of catalytic cracking (Table 3). 15 cm ^{3 of} catalyst diluted with SiC were charged into a tubular reactor to a total volume of 30 cm ³ . Sulfidation was carried out with a mixture of dimethyl disulfide and a kerosene fraction at 240 ° C for 10 hours and at 340 ° C for 8 hours. Test conditions: hydrogen pressure 1.0-3.0 MPa, hydrogen circulation rate of 50-300 nl / l of raw material, the volumetric feed rate of 5.0-10.0 h ^-1 , the temperature in the reactor 280-320 ° C.

Hydrogenates were separated from hydrogen in high and low pressure separators, then they were treated with 10% NaOH solution for 15 minutes, washed with distilled water until the washings were neutral, dried over calcined CaCl ₂ during the day. The sulfur content in the feed and the resulting hydrogenates was determined according to GOST R 52660, the olefin hydrocarbon content according to GOST 2070, the fractional composition according to GOST 2177-99, the octane number by research method according to GOST 8226.

The test results of the catalysts are presented in table. 3.

Table 3 Characteristics of the process of selective hydrotreating gasoline fractions of catalytic cracking in the presence of the claimed catalysts and prototype Catalyst number Characteristics of raw materials ¹ Process conditions ² The content in the stable hydrogenate,% wt. Process indicators NK, ° C KK, ° C Content,% wt. T, ° C ISPS, h ^-1 R, MPa H ₂ / feed, nl / l sulfur OU S.F. Δ OFP sulfur OU one 0.1024 5.7 1.71 -5.0 2 0.0168 6.4 8.24 -2.5 5 120 218 0.2018 8.7 320 5,0 3.0 300 0,0326 6.8 7.58 -2.2 6 0,0334 6.9 7.95 -1.5 7 0.0130 6.7 10.67 -2.0 110 220 0.0096 13.5 280 10.0 1,5 one hundred 0.0020 13.5 - 0,0 7.5 0.0014 13,2 85.67 -0.1 5,0 0,0005 12.3 31.74 -0.3 9 120 218 0.2018 8.7 320 5,0 3.0 300 0.0150 7.0 12.16 -1.6 110 220 0.0096 13.5 280 10.0 1,5 150 0.0022 13.5 - 0,0 7.5 1,0 fifty 0.0031 13.5 - 0,0 ¹ - NK - the beginning of boiling, KK - the end of boiling, OS - olefinic hydrocarbons.
² - T - temperature, ISPS - volumetric feed rate, P - pressure.
³ - S.F. - the selective factor calculated by the formula 1, Δ OF - the difference between the octane number of the stable hydrogenate and raw materials.

The inventive catalysts are superior in activity and selectivity to the prototype. The process indicators during the hydrotreating of gasoline obtained from crude vacuum gas oil (with a sulfur content of 0.2018% wt.) Allow us to conclude that the catalysts and their preparation methods are highly effective. The process of hydrotreating olefin-containing hydrocarbon feedstocks in the presence of the inventive catalysts ensures the production of gasoline with an ultra-low sulfur content and maintaining its octane number at the initial level.

Claims (14)

1. A catalyst for the selective hydrodesulfurization of an olefin-containing hydrocarbon feed, consisting of metal compounds of Co or Ni, Mo and Na or K, supported on a carrier, characterized in that it contains a bimetallic complex compound of metals of Co or Ni, Mo and Na or K, a carboxylic acid containing at least one carboxyl group and 1-20 carbon atoms; the catalyst has a specific surface area of 180-350 m ² / g, a pore volume of 0.3-1.1 cm ³ / g, an average pore diameter of 5.5-11.0 nm. 2. The catalyst according to claim 1, characterized in that the carrier is alumina, silica, or a composition thereof. 3. The catalyst according to claim 1, characterized in that the bimetallic complex compound contains at least one of the following heteropolyanions [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [Co (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [ Ni (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [P ₂ Mo ₅ O ₂₃ ] ^6- , [SiMo ₁₂ O ₄₀ ] ^4- , [PMo ₁₂ O ₄₀ ] ^3- , while the content in the MoO ₃ catalyst calcined at 550 ° C is 14.0-23.0 wt.%, CoO or NiO - 4.0-6.5 wt.%, Potassium oxide (sodium) - 5-10 wt.%. 4. The catalyst according to claim 1, characterized in that it has the form of cylinders or trefoils. 5. A method of preparing a catalyst for selective hydrodesulfurization of an olefin-containing hydrocarbon feed according to claim 1 by impregnating the carrier with a solution of the precursors of the active component, characterized in that the carrier is once impregnated with an aqueous solution having a pH of 2.5-4.0, containing at least one of the hetero-polyanions of the series [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [Co (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^{6 -} , [P ₂ Mo ₅ O ₂₃ ] ^6- , [SiMo ₁₂ O ₄₀ ] ^4- , [PMo ₁₂ O ₄₀ ] ^3- , one of the series cobalt hydroxide Co (OH) ₂ ∙ nH ₂ O is used as a cobalt compound (n = 0.5-5), cobalt carbon dioxide CoCO ₃ basic cobalt 2CoCO ₃ ∙ 3Co (OH) ₂ ∙ nH ₂ O (n = 0.5-5), any of the series potassium hydroxide KOH, potassium carbonate K ₂ CO ₃ , sodium hydroxide NaOH , sodium carbonate Na ₂ CO ₃ , a carboxylic acid containing at least one carboxyl group and 1-20 carbon atoms is used as a stabilizer for the impregnating solution. 6. The method of preparation of the catalyst according to claim 5, characterized in that the heteropolyanion [P ₂ Mo ₅ O ₂₃ ] ^6- or [PMo ₁₂ O ₄₀ ] ^{3- is} formed by sequentially dissolving the molybdenum oxide MoO ₃ or molybdenum acid H ₂ MoO ₄ in 85% phosphoric acid H ₃ PO ₄ and the addition of a 30% solution of H ₂ O ₂ at a temperature of 50-90 ° C and a pH of 1.0-1.5 in ratios corresponding to stoichiometry in a heteropolyanion. 7. The method of preparation of the catalyst according to claim 5, characterized in that one of the heteropolyanions [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [Co (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^{6- is} formed by sequentially dissolving molybdenum oxide MoO ₃ or molybdenum acid H ₂ MoO ₄ in a 30% hydrogen peroxide solution at a temperature of 50-90 ° C, s the subsequent addition of a Co or Ni salt in proportions corresponding to stoichiometry in the heteropolyanion. 8. A method of preparing a catalyst according to any one of claims 5, 6 or 7, characterized in that citric acid is used as a stabilizer. 9. The method of preparation of the catalyst according to any one of paragraphs.5, 6 or 7, characterized in that either the impregnation of the carrier by moisture capacity or from excess solution is used. 10. The method of preparation of the catalyst according to any one of paragraphs.5, 6 or 7, characterized in that the impregnation of the granules of the carrier is carried out after creating a vacuum in a vessel containing a carrier. 11. The method of preparation of the catalyst according to any one of paragraphs.5, 6 or 7, characterized in that the impregnation of the granules of the carrier after creating a vacuum is carried out with an impregnating solution at temperatures of 20-50 ° C. 12. The method of preparation of the catalyst according to any one of claims 5, 6 or 7, characterized in that after impregnation, the catalyst is dried at a temperature of 120-180 ° C in a stream of air or nitrogen. 13. A process for the selective hydrodesulfurization of an olefin-containing hydrocarbon feed, which comprises passing an olefin-containing hydrocarbon feed through a catalyst bed, characterized in that a catalyst according to any one of claims 1 to 4 or a catalyst prepared by any of the methods of claims 5 to 12 are used. 14. The process according to p. 13, characterized in that it is carried out at a temperature of 220-320 ° C, a pressure of 0.5-3.0 MPa, a volumetric flow rate of raw materials 4-12 h ^-1 , a volumetric ratio of hydrogen / raw material 50-300 m ³ / m ³ .