Catalyst, method of preparation thereof, and a diesel fraction hydrodesulfurization process

FIELD: petroleum processing catalysts.

SUBSTANCE: invention relates to catalysts for deep processing of hydrocarbon stock and can be employed in petroleum processing and petrochemical industries. Particularly, invention provides catalyst for diesel fraction hydrodesulfurization process, which contains, as active component, oxygen-containing molybdenum and cobalt and/or nickel complex compound at Mo/(Co+Ni) atomic ratio 1.5-2.5 and is characterized by specific surface 100-190 m2/g, pore volume 0.3-0.5 cm3/g, prevailing pore radius 80-120 Å. Catalyst support is constituted by alumina or alumina supplemented with silica or montmorillonite. Described are also catalyst preparation procedure and diesel fraction hydrodesulfurization process.

EFFECT: increased catalytic activity and resistance of catalyst against deactivation in presence of diesel fuel hydrocarbon components and sulfur compound of thiophene and its derivatives series.

8 cl, 1 tbl, 7 ex

 

The invention relates to the field of chemistry, and in particular to catalysts designed for deep Hydrotreating of hydrocarbons, in particular diesel fractions from sulfur compounds of the number of thiophene and its derivatives: benzothiophene, studied, alkylbenzoates and 4.6-dialkyldimethyl, and other serosoderjaschei aromatic compounds, and can be used in the refining and petrochemical industries.

Known Co-Mo and Ni-Mo catalysts containing 8-10 wt.% Moo3and 3 wt.% COO or NiO deposited on a porous alumina carriers provide effective cleaning of diesel fractions from sulfur compounds, mainly from mercaptans, diallyldisulfide, thiophene and some of its derivatives, up to a level of 500 ppm sulfur. Sulfur remaining in diesel fractions after hydrodesulphurization unit on the above catalysts, is part of the most stable organic sulfur compounds, such as substituted alkylbenzoates with one or two alkyl groups, located in the β-position to the sulfur atom. Therefore, the conversion of the substituted alkylbenzoates determines the degree hydrodesulphurization unit of raw material in the processes of deep Hydrotreating of diesel fractions.

One way to achieve deep hydrodesulphurization unit diesel fractions is increased pressure is occurring and the process temperature, allowing the use of the process known Co(Ni)-Mo(W) catalysts. However, increasing the pressure and temperature of the process leads to deactivation of the catalysts due to an increase in the partial pressure of hydrogen sulfide in the gas mixture, particularly for Ni-Mo catalyst, and by zakoksovanie the catalyst surface hydrocarbon components of diesel fuel. The disadvantage of this method is also increasing kekirawa activity of Co(Ni)-Mo(W) catalysts at elevated temperatures, which inevitably leads to a decrease of the yield of liquid fraction and lower cetane number.

Other ways to ensure the high level of hydrodesulphurization unit is the optimization of the catalyst composition. It is known that in the case of β-dialkyldimethyl the rate of conversion on the route hydrogenolysis connection C-S slows to a crawl due to the strong steric at their adsorption on the surface of the active centre. Therefore, for carrying out processes of deep hydrodesulphurization unit you want to use media with a developed specific surface (not below 200 m2/g), pore structure (0.5 to 0.9 cm3/g) and narrow distribution of pore size, while the share of pore size 75-130 Å must be at least 75% of the total pore volume (US 3840472, B01J 27/19, C10G 45/08, 8.10.74; 2003/0173256; 4818743, B01J 23/85, 04.04.89; 489265, B01J 23/24, 07.11.89). Removal of steric hindrance arising from adsorption β-dialkyldimethyl, is achieved by optimizing the composition of the active complex, in particular by increasing the number of so-called "CoMoS II centers, consisting of a sulfide of molybdenum, MoS2having a layered structure, doped perimeter promoter cations, Co or Ni. The increase in the number of "CoMoS II centers is usually achieved by increasing the content of compounds of molybdenum in the catalyst to 18-22 wt.% (US 2003/0173256), and in some cases up to 29 wt.% (US 2006/0054536). In the preparation of catalysts with a high content of active complex by impregnation inevitably raises the problem of its distribution within the medium (up to 6 atoms of Mo on nm2Al2About3) impregnation of concentrated solutions. The uniformity of application of the active complex is typically accomplished by regulation of the pH and composition of the impregnating solutions by introducing them in acid additives, such as H3PO4and other (US 3755196, 4392985, 4879265). The composition and pH of the impregnating solution should be selected so as to exclude the formation of cristallizing phases Co3O4and CoAl2O4when the heat treatment of the catalyst, since the latter when the pretreatment of the catalyst in structuresa environment (sulfatirovaniu) TA which are stated in the sulfide of cobalt, Co9S8inactive in the reaction hydrodesulphurization unit. Education cristallizing phases Co3O4and CoAl2O4decreases in the presence of an impregnating solution of organic additives, such as citric acid (US 2003/0173256, 2006/0054536), when the heat treatment of the catalyst at temperatures not higher than 200° (US 2003/0173256, 2006/0054536) and sulfatirovaniu catalyst in soft conditions (US 4879265, 2003/0173256).

For preparation of the impregnating solutions typically use the oxides of molybdenum and tungsten, ammonium salts of molybdenum and tungsten acid (paramolybdate and paraformat ammonium), molybdenum or tungsten acid, in some cases phosphorus-molybdenum or phosphorus-tungsten acid. In order to increase the solubility of compounds of molybdenum and tungsten in water in the impregnating solutions add mineral acids, mainly of phosphoric acid and phosphoric acid. Additives of mineral acids can also increase the stability of the joint impregnating solutions containing compounds VIII and VI groups, agglomeration and precipitation cristallizing precipitation. Another way of increasing the solubility of the compounds of molybdenum and tungsten and sustainability joint impregnating solutions containing compounds VIII and VI groups is the use of concentrated aqueous solutions amiocap as compounds precursors of cobalt and Nickel are used as water-soluble, and poorly soluble compounds, most often it is the nitrate, sulfate, acetate, citrate, carbonate, hydroxide and oxide of cobalt and/or Nickel. The main disadvantage of joint impregnating solutions containing metal compounds VIII and VI groups and phosphoric acid, is their low stability in the presence of nitrate-anion (NO3-undesirable presence in General, US 3840472) and cation ammonium (not more than 1.5 mol/l, US 3840472). For example, the excess ion-ammonium interacts with VI and VIII metals of groups and phosphoric acid with the formation of cristallizing precipitation of phosphate of cobalt(Nickel), and ammonium or ammonium salts of phosphorus molybdenum acid.

Supplementation of phosphoric acid in the impregnating solution containing metal salts VI and VIII groups of the Periodic table, allows to increase the solubility of compounds of molybdenum (in the form of oxide or paramolybdate ammonium) in aqueous solutions, and therefore allows you to enter a catalyst in a high concentration of molybdenum in the range 17-27 wt.% Moo3one impregnation. However, the ratio R/Mo and pH of the impregnating solution containing metal salts VI and VIII groups of the Periodic table, have a significant impact on gidroobesserivaniya activity of Co(Ni)-Mo(W) catalysts. On the one hand, the use of solutions of salts of metals of the VI and VIII groups, stable welding temperature, avannah phosphoric acid, ensures uniform deposition of the active component on the surface of the carrier and excludes education cristallizing units of the active component on the carrier surface, which allows to improve gidroobesserivaniya activity of Co(Ni)-Mo catalysts. Thus, the content of phosphate ion in an impregnating solution containing metal salts VI and VIII groups, should be sufficient to ensure dissolution of the required number of precursors of the active component and the stability of the joint impregnating solution.

On the other hand, the content of phosphate ion in the impregnating solution should not be excessive, as this can lead to decrease in activity for several reasons. First, the pH of the impregnating solution should not be significantly higher than 2 because of the high pH value leads to the formation and deposition on the surface of the carrier of the active component in the form of cristallizing particles or crystallites. Secondly, the pH of the impregnating solution should not be significantly below 1, since low pH value leads to the interaction of phosphate ion with the surface of the aluminum oxide and peptization, which leads to the reduction of the specific surface of the carrier available for deposition of the active component, and the formation of aluminum phosphate. In addition, excess phosphate ion may means the ü chemical destruction of the active complex by calcination, in particular, the formation of cobalt aluminate(Nickel).

In the patent US 3840472, B01J 27/19, 8.10.1974 invited to prepare an impregnating solution to use molybdenum oxide and one of the components of metals of group VIII of the Periodic system, selected from a carbonate, hydroxide, acetate, formate, oxide in solid form, dissolving them in phosphoric acid at the following concentrations of 0.3 to 2.5 mol/l, R, 0.4 to 1.5 mol/l of a metal of group VIII and 1-3 mol/l Mo.

The close method of preparation of the catalyst described in patents US 4500424, 19.02.1985; 4818743, B01J 027/185, 4.04.1989. The catalyst is prepared by impregnating gamma-alumina with a solution containing molybdenum oxide, cobalt carbonate and phosphoric acid, in an amount necessary for the introduction of the catalyst is not less than wt.%: 17-25 of Moo3, 1-6 COO or NiO, and 1-4, R, provided that the molar ratio P/Moo3in the solution above 0,1, mainly of 0.2 pH in the range 0-1,0. The patent also States that in the case of paramolybdate ammonium, as a precursor of cobalt is better to use nitrate of cobalt (Nickel). In the case of molybdenum oxide as the precursor of cobalt is better to use the carbonate cobalt (Nickel).

In patents US 3755150, 3755196, 28.08.1973; 4686030, 11.08.1987 and 4846961, 11.07.1989 describes catalysts which are obtained by impregnation of alumina, including modified the second silicon solutions of salts of active metals (Mo, Ni, Co) with the introduction of impregnating a solution of phosphorus compounds in the form of phosphoric acid. Increased stability of the impregnating solution containing paramolybdate ammonium and nitrate Nickel (cobalt), is achieved by introducing into the solution of phosphoric acid to the mass ratio R/Moo3in the range of 0.1 to 0.25 and a pH in the range of 1-2. After annealing at 900°F catalyst hydrodesulphurization unit contains, wt%: 5-40 NGO3(mainly 15-21,7), 1-10 NiO or COO (mainly 2,8-3,07) and 2,4-3,5 R, plotted on the modified silicon Al2About3.

In the patent US 4392985, B01J 027/14, 12.07.1983 to obtain stable impregnating solution containing paramolybdate ammonium and nitrate cobalt (Nickel), it is proposed to enter into a solution of phosphoric acid to mass ratio R/Moo3in the range of 0.05-0.16 and pH lower than 1.2. Impregnating solution is stable provided that the content is not less than 17 wt.% Moo3and the mass ratio of COO/Moo3in the range of 0.1-0.4.

The effect of phosphate ion on the activity of catalysts for hydrodesulphurization unit smoothes adding in an impregnating solution of organic compounds such as citric acid. In the patent US 4879265 B01J 027/19, 7.07.1989 described method of preparation of a highly active catalyst containing not less, wt.%: 17 Moo3(27), 1 R (4) and 0.5 NiO (up to 5). It is talization prepare the impregnation solution, contains phosphate ion and citric acid, while maintain the pH of the solution is less than 1.0 and the molar ratio of citric acid to metal of group VIB in the range of 0.5 to 0.9/1, followed by drying and calcination at a temperature of not lower than 750°F, mostly 1000°F. To prepare mainly use paramolybdate ammonium and nitrate cobalt (Nickel), but it is possible to use the oxide of molybdenum and an oxide or carbonate of cobalt (Nickel). During annealing the catalyst for the most part citric acid decomposes, is not more than 0.5 wt.% C. the Catalyst has a high activity in the processes hydrodesulphurization unit and Hydrotreating.

In all known methods is rather high concentration of phosphate ion in the impregnating solution, which provides a high phosphorus content in the catalyst (2.4 to 3.5 wt.% P, US 3755150, 3755196, 4392985, 4846961 and others), and increases the acidic properties of the catalyst. The main disadvantage of these catalysts is not sufficiently high stability of the catalyst to the effects of high temperatures and lack of high activity in the process for hydrotreatment of diesel fractions in the processing of high-sulphur crude oil.

Closest to the technical nature of the claimed and achieved result is the catalyst described in patent application 2006/0054536, 16.03.2006. Catalysis is the PR of the prototype is prepared by impregnating alumina carrier, containing 1 wt.% SiO2or 5 wt.% ultrastabilized zeolite Y with a molar ratio of SiO2/Al2O3equal to 6, an aqueous solution containing cobalt citrate, phosphoric acid (85%solution) and molybdophosphoric acid and having a pH in the range of 0.48-0,54, followed by drying in a stream of nitrogen and heat-treated in a stream of air at 120°within 12 hours After heat treatment at 120°the catalyst contains, wt%: 10-40 NGO3mainly 26,2-29, 1-15 COO and/or NiO, mainly 5,6-5,8, 1,5-8 P2O5mainly 3,6-5,5, and 2-14, applied to the extrudates γ-Al2About3that γ-Al2About3with SiO2(99/1) or γ-Al2About3with zeolite Y (95/5). The catalyst has high gidroobesserivaniya activity at a pressure of 4.9 MPa, space velocity of 1.5 h-1and the ratio of hydrogen/feedstock 200 and a temperature of 350°and sulfur in the raw materials of 1.61 wt.%, providing a residual sulfur content at the level of 8-10 ppm.

The main disadvantage of this catalyst is its high content of phosphorus, which leads to a fairly rapid deactivation of the catalyst due to coking of the hydrocarbon components of petroleum fractions, particularly when exposed to elevated temperatures, and the lack of a high activity in the process for hydrotreatment of diesel fractions when added is de high-sulphur crude oil with a low partial pressure of hydrogen.

The problem solved by the invention: developing composition and method of preparation of the catalyst intended for carrying out processes of hydrodesulphurization unit sour diesel fractions on existing hydrotreatment units.

This is achieved by optimizing the composition and method of preparation of the catalyst containing complex compounds of molybdenum and cobalt dispersed on the surface of the alumina carrier, including a modified acid supplements. The content of compounds of molybdenum in the amount of 14-29, preferably 16 to 21 wt.% Moo3and the ratio of Mo/Co(Ni) in the range of 1.5 to 2.5 is sufficient to ensure high activity in the process of diesel hydrodesulphurization unit fractions containing 1.06 wt.% sulfur at temperatures 320-350°C, pressure of 3.5 MPa and a ratio of hydrogen-containing gas 300 m3/m3of raw materials.

A distinctive feature of the proposed catalyst is the absence in the composition of the catalyst of phosphorus, which improves the stability of the catalyst by coking of the hydrocarbon components of diesel fractions. For dissolution of molybdenum oxide and cobalt carbonate in an amount to provide application 14-29 wt.% Moo3and 3-8 wt.% Soo, in the impregnating solution was added a mixture of complexing organic acids, in particular of lemon the th and breast and/or malonic, acetic, formic acids. When this molar ratio Coco3/citric acid in the impregnating solution should be at least 3/2, and the pH of the impregnating solution is in the range of 1.7 to 2.7, which provides dissolving the required quantity of molybdenum oxide and cobalt carbonate and the stability of the impregnating solution.

The use of an impregnating solution containing complex compounds of molybdenum and cobalt (Nickel), stabilized with a mixture of complexing organic acids, which helps to eliminate the interaction of compounds of cobalt with aluminum oxide in the stages of impregnation and, consequently, the formation of Co3O4and CoAl2O4during annealing. The lack of Co3O4and CoAl2O4recorded according to the electronic spectroscopy, in particular for low-intensity bands in the region of 15000 cm-1(multiplet), corresponding to d-d transitions of cobalt cations With2+in a tetrahedral environment. In addition, the slow drying of the impregnated carrier in a stream of inert gas or air atmosphere allows you to avoid crystallization of the active complex, and the calcination in a stream of air at temperatures below 240°excludes active destruction complex.

The media, and hence the catalyst is predominantly made in the form of extrudates - tsilindrovymi of trilistniku, with a diameter of 1.0 to 1.5 mm and a length of 3-5 mm Using extrudates in the form of "trilistnika also allows to increase the efficiency of oil hydrodesulphurization unit fractions.

The above method of preparation of the proposed catalyst can increase the activity of Co-Mo catalyst diesel hydrodesulphurization unit fractions at temperatures 320-350°C, pressure of 3.5 MPa, and the ratio of the circulation of the hydrogen-containing gas 300 m3/m3raw materials and the stability of the catalyst to deactivation in the presence of organic serosoderjaschei compounds at elevated temperatures and, therefore, to use the catalyst in the processes of diesel hydrodesulphurization unit fractions on the existing equipment. Along with the activity and stability in the reactions of transformation of sulfur compounds, the catalyst provides the resulting diesel fuel required cetane number, distribution fractions according to boiling points, density, content of aromatic and polyaromatic compounds. Described variant of the catalyst is preferred for processes of diesel hydrodesulphurization unit fractions.

The process for hydrotreatment of diesel fractions in industrial installations carried out at a temperature 340-400°C, the pressure of 3-3 .5 MPa and 5.2-5.5 MPa in the case of Co-Mo and Ni-Mo catalysts, respectively, and the ratio of circulation in dartsdeluxe gas 250-350 m 3/m3of raw materials. The concentration of sulfur compounds in diesel fractions is usually ˜1-1,5 wt.% in terms of elemental sulfur. In accordance with this selected conditions testing of catalysts.

The catalysts are tested in the form of fractions of size 0.25-0.5 mm, which is prepared by crushing and dispersion of the source of the extrudates. A portion of the catalyst mass of 2.0 g placed in a vertical flow reactor made of stainless steel having an inner diameter of 8 mm, while the height of the catalyst layer is 50±10 mm Above the catalyst layer for uniform mixing and heating of the feedstock is placed a layer of silicon carbide (particle 1-2 mm), which is separated from the catalyst layer pad of fiberglass. Lower catalyst layer to fill the free volume of the reactor was placed a layer of quartz (particle 1-2 mm), which is also separated from the catalyst layer pad of fiberglass.

Catalysts sulfiderich at atmospheric pressure in a stream of hydrogen sulfide, which begin to serve it at room temperature at a rate of 1 l/hour, the Reactor is heated from room temperature to 400°C for 30 min and then continue sulfatirovnie for 2 hours and Then the reactor by means of shut-off valves are cut off simultaneously from the supply lines and discharge of hydrogen sulfide and cooled to room temperature.

p> As a source of raw materials use of straight-run diesel fuel having the following characteristics:

Density at 20° - 844 kg/m3

Cetane number - 53,5±0,5

The pour point of about -10°

The sulfur content was 1.06% S (10600 ppm)

Flash point (closed Cup) - 66,9°

Fractional composition:

- 50% of the volume distills at 292°

- 96% of the volume distills at 366°C.

The reactor solifidianism catalyst is placed in a thermostat electric heating, filled with hydrogen to a pressure of 3.5 MPa at room temperature, then start the supply of diesel fuel, providing bulk fuel 2 h-1and regulating the flow of hydrogen to the volume ratio of hydrogen/diesel fuel, equal to 300. At the moment when the costs of reagents stabilized, begin heating the reactor from room temperature to 340°With that carried out for 35-40 minutes Next process is carried out at a temperature of 340°and a pressure of 3.5 MPa.

At the exit of the reactor, the products pass through the capillary stainless steel, internal diameter 2 mm, which is cooled to 60-70°With, then go on the site to reset the pressure to atmospheric. Further, the products are cooled in the refrigerator separator, provided with a water jacket, and is divided into gas and liquid sostav the matter. The entrainment of liquid gas does not exceed 1 wt.%. Products accumulated during the first 3 h after the beginning of the rise of temperature in the reactor, is discarded without any analysis, then every 2 h to determine the mass output of diesel fuel and the sulfur content in it.

About the activity of the catalyst is judged by the content in the residual oil sulfur. Mass content of sulfur in liquid petroleum products determine without first removing dissolved therein sulfide. To determine the sulfur content using x-ray fluorescence analyzer HORIBA SLFA-20, allowing to work in the concentration range S from 20 ppm to 5 wt.% with an accuracy of 5 ppm. Specially experiments for hydrogen sulfide removal using 10%aqueous NaOH solution (mixed with a sample of 1 to 1) show that dissolved in the oil hydrogen sulfide can vary within 20-80 ppm.

To assess the deactivation of the catalyst due to coking of the hydrocarbon components and sulfur-containing compounds in diesel fractions catalysts exposed to elevated temperatures of 370°With 6-9 h (to speed up the processes of decontamination), and then measure the activity of catalysts at a temperature of 340°C, pressure of 3.5 MPa and a ratio of hydrogen/feedstock - 300.

The invention is illustrated by following the existing examples.

Example 1

For preparation of the impregnating solution to of 5.89 g of cobalt carbonate, Soso3add 42 ml of distilled water and heated to 80°C. Then with stirring portions 6,93 g of citric acid monohydrate, CH2S(HE)CH2(COOH)3·N2O while watching intense emission of CO2. Waiting for the complete dissolution of the precipitate, add 12,14 g of molybdenum oxide Moo3and 4 ml of 80%lactic acid, NOSEIN3COOH. Continue to stir the solution at 80°until dissolved. After dissolution, the solution volume of 50 ml Solution was characterized by a pH of 2.4, the content of Moo3- 19 wt.% and a molar ratio of Mo/Co, equal to 1.7.

As the carrier used extrudates of alumina with a diameter of 1.3-1.4 mm and a length of 4-5,2 mm, having a specific surface 275-295 m2/g, pore volume of 0.82 cm3/g and average pore 119 Ådetermined from adsorption isotherms of nitrogen. The share of pore size 70-130 Å 65% of the total pore volume.

To 30 g of the calcined extrudates add 27 ml of impregnating solution and incubated for 15 minutes Impregnated extrudates are dried at room temperature in a stream of nitrogen and subjected to heat treatment in a stream of nitrogen at 150°C for 10 hours

The content of molybdenum oxide in the catalyst is 16.2 wt.% (in the estuaries and the ü and then, based on Moo 3), cobalt oxide - 4.7 wt.% (here and further in the calculation of the Soo). The catalyst has a molar ratio of Mo/Co - 1,8.

The catalyst after heat treatment at 150°has a specific surface area (Sbeats) - 113 m2/g, pore volume (V) - 0,35 cm3/g and the average radius of the pore (Dcp) - 122 Ådetermined from adsorption isotherms of nitrogen. The catalyst has a narrow pore size, the pore size Dcp±15 Å 70% of the total pore volume. In the electronic spectra of diffuse reflection, the catalyst is characterized by absorption bands in the area 12400-14000 cm-1and 14200-18500 cm-1corresponding to d-d transitions Mo5+and Co2+Ohin complex compounds.

Of the extrudates of catalyst prepared fraction size of 0.2-0.5 mm Fraction in the amount of 2 g is loaded into the reactor and subjected to solifidian in the stream of hydrogen sulfide at 400°C for 2 hours

Determine the yield of liquid oil and sulfur contents, which provide sulpicianus catalyst feeding him straight-run diesel fuel with a content of 1.06 wt.% sulfur and the following process conditions: a temperature of 340°C, pressure of 3.5 MPa, mass flow rate of diesel fuel 2 h-1and a volume ratio of hydrogen/diesel fuel 300.

Under these conditions, the process is Hydrotreating diesel fuel catalyst enables the reduction of sulfur in liquid petroleum products to the level of 200-245 ppm and the yield of liquid oil products at the level of 96-97%.

After 24 h raise the temperature in the reactor to 370°and determine the sulfur content in the liquid petroleum products, the content of sulfur in liquid petroleum products is reduced to the level of 55-60 ppm.

After 9 hours, reduce the temperature in the reactor to 340°and determine the sulfur content in the liquid petroleum products. The catalyst provides the sulfur content in the liquid petroleum products at the level of 295-325 ppm.

Example 2

Similar to example 1, except for preparing an impregnating solution using 5,74 g of cobalt carbonate, 6,76 g of citric acid monohydrate, 13,88 g of molybdenum oxide, 2 ml of lactic acid (80%solution) and 2 ml of acetic acid. The solution has a pH - 2,95, contains 21 wt.% Moo3and the molar ratio of Mo/Co - 2,0. As media use aluminum oxide with addition of zeolite H-mordenite in the ratio of 90/10.

The impregnation, drying and heat treatment is carried out in the conditions of example 1. The catalyst after calcination at 150°contains, wt%: 19,0 of Moo3and 4.8 Soo.

The catalyst after calcination at 150°has a specific surface area of 104 m2/g, pore volume of 0.35 cm3/g and average pore 98 Å.

Under the conditions of test example 1, the catalyst provides a 97% yield of liquid oil and the sulfur content in them at the level of 210-230 ppm at 340°C.

Example 3

Similar to example 1, except for preparing ropetackle solution using 4.09 g of cobalt carbonate and 1.69 g of Nickel carbonate, 6.8 g of citric acid monohydrate, 16.7 g of molybdenum oxide, 2 ml of lactic acid (80%solution) and 1.0 g of malonic acid. The solution has a pH - 2,85, contains 24 wt.% Moo3and the molar ratio of Mo/(Co+Ni) is 2.4. As the carrier used the aluminum oxide with the addition of montmorillonite in the ratio of 90/10.

The impregnation, drying and heat treatment is carried out in the conditions of example 1. The catalyst after heat treatment contains, wt%: 20.5 Moo3, 3,4 Soo and 1.3 NiO.

The catalyst after heat treatment has a specific surface 116 m2/g, pore volume of 0.35 cm3/g and average pore 105 Å.

Under the conditions of test example 1, the catalyst provides a 98% yield of liquid oil and the sulfur content in them at the level of 250-270 ppm at 340°C.

Example 4 (comparative prototype)

To prepare an impregnating solution of 42 g of distilled water add 11,64 g of cobalt citrate and is 1.82 g of phosphoric acid (85%solution), heated to 80°C and stirred for 10 minutes Then add 17,74 g of phosphorus molybdenum acid and stirred at the same temperature until complete dissolution. The resulting solution has a pH - value of 0.52, contains 24 wt.% Moo3the ratio Mo/Co - 2,4, R/Mo 0,2.

As the carrier used extrudates of alumina of example 1. The impregnation, drying and heat treatment is carried out in the conditions of example 1.

The catalyst contains, wt%: 21,3 of Moo3, 4.6 cobalt oxide, 1,2 phosphorus.

The catalyst after calcination at 150°has a specific surface area (Sbeats) - 150 m2/g, pore volume (V) - 0,31 cm3/g and the average radius of the pores (Dcp) - 85 Å.

Under the conditions of test example 1, the catalyst provides a 96% yield of liquid oil and the sulfur content in them at the level of 380-400 ppm at 340°C.

Example 5 (comparative 1)

For preparation of the impregnating solution to 9,03 g of cobalt carbonate add 42 ml of distilled water and heated to 80°C. Then with stirring portions 10,63 g of citric acid monohydrate, while there has been intense emission of CO2. Waiting for the complete dissolution of the precipitate, add 26,28 g of molybdenum oxide Moo3and of 4.95 tons of phosphoric acid (85%solution). Continue to stir the solution at 80°until dissolved. After complete dissolution the solution volume is 50 ml, has a pH of 0.75, contains 27.5 wt.% Moo3and has a molar ratio Mo/ - 2.4 and P/Mo - 0,38.

As the carrier used extrudates of alumina of example 1. The impregnation, drying and heat treatment is carried out in the conditions of example 1. The catalyst after heat treatment contains, wt%: 23 Moo3, 4,4 Soo and 1,1 R.

The catalyst after calcination at 150&#HVS has a specific surface 114 m2/g, pore volume - 0,31 cm3/g and average pore - 108 Å.

Under the conditions of test example 1, the catalyst provides a 96% yield of liquid oil and the sulfur content in them at the level 365-400 ppm at 340°C.

Example 6 (comparative 2)

Analogous to example 5, but to prepare an impregnating solution use of 5.82 g of cobalt carbonate, at 6.84 g of citric acid monohydrate, 17,95 g of molybdenum oxide and 1.34 g of phosphoric acid (85%solution). The solution has a pH of 2.45, contains 24 wt.% Moo3and the molar ratio of Mo/Co - 2.4 and R/Mo is 0.1.

The catalyst after heat treatment at 150°contains, wt%: 21.1 Moo3, 5,5 Soo and 0.43 P and has a specific surface 116 m2/g, pore volume - 0,31 cm3/g and average pore - 105 Å.

Under the conditions of test example 1, the catalyst provides a 96% yield of liquid oil and the sulfur content in them at the level of 280-370 ppm at 340°C.

Example 7 (comparative 3)

Analogous to example 5, but to prepare an impregnating solution using 6.0 g of cobalt carbonate, 17,55 g of molybdenum oxide and a 4.53 g of phosphoric acid (85%solution). The solution after dissolution has a pH of 2.45, contained 24 wt.% Moo3and the molar ratio of Mo/Co - 2,3 and P/Mo - 0,24.

The catalyst after calcination at 150°contains, wt%: 21 Moo3, 5,3 Soo 1,2 and R; is the specific surface is gnosti - 144 m2/g, pore volume - 0,40 cm3/g and average pore - 108 Å.

Under the conditions of test example 1, the catalyst provides a 96% yield of liquid oil and the sulfur content in them at the level of 360-380 ppm at 340°C.

It is seen that the inventive compositions of catalysts containing predominantly 16-21 wt.% Moo3and 4-6 wt.% Soo, provided the molar ratio Mo/(Co+Ni) in the range of 1.5 to 2.5 and made with impregnating solutions, stabilized with a mixture of complexing organic acids such as citric and lactic (example 1), and acetic acid (example 2) or malonic (example 3), provide a higher degree of diesel hydrodesulphurization unit fractions compared with catalysts prepared from impregnating solutions containing phosphate ion (examples 4-7). At a pressure of 3.5 MPa, mass flow rate of diesel fuel 2 h-1and a volume ratio of hydrogen/fuel 300 of the inventive catalysts provided the Hydrotreating of diesel fuel sulfur compounds at the 97.5 98.1 per cent at a temperature of 340°and at the level of 99.3-99.7% of at 370°C. the content of sulfur remaining in diesel fuel after hydrodesulphurization unit at 340°and 370°is not more than 250-270 35-70 ppm and ppm, respectively (together with hydrogen sulfide dissolved in the liquid oil, the content of which ranged from 20-80 pm).

Assuming the introduction of impregnating a solution of a mixture of organic complexing acids in an amount to provide a pH in the range of 1.7-2.7 and the molar ratio Coco3/citric acid is not lower than 3/2, is provided by dissolving the required quantity of molybdenum oxide and cobalt(Nickel) carbon and sustainability of the impregnating solution. The exception of phosphorus in Co(Ni)-Mo catalyst, usually injected in the catalyst composition in a molar ratio P/Mo - 0.2 and above, can improve the stability of the catalysts for the decontamination of hydrocarbon components of diesel fractions, including sulfur compounds, as is shown by data on exposure to elevated temperatures of the process hydrodesulphurization unit of diesel fuel. After exposure to a temperature of 370°C for 7-9 h of the claimed compositions of the catalyst provided at 340°With removal from diesel fuel sulfur compounds to the level of 315-350 ppm sulfur, while for phosphate (P/Mo≥0.2) catalysts was achieved level 420-460 ppm of sulfur.

The described method of preparation and composition of the proposed catalyst allows to increase the activity of Co-Mo catalyst diesel hydrodesulphurization unit fractions under conditions that are close to existing industrial installations for hydrotreatment of diesel fuel: a temperature in the range of 340-400°With pressure 3,0-3,7 MPa and the ratio of the circulation of the hydrogen-containing gas 300 m 3/m3raw materials, as well as to increase the stability of the catalyst to deactivation in the presence of hydrocarbon components of diesel fuel and sulfur compounds of the number of thiophene and its derivatives at elevated temperatures. This allows the use of the catalyst in the processes of diesel hydrodesulphurization unit fractions on the existing equipment. Described variant of the catalyst is preferred for processes of diesel hydrodesulphurization unit fractions.

Table

The chemical composition and textural characteristics of the catalysts of the proposed structure and their catalytic properties defined in the Hydrotreating process of straight-run diesel fuel at a temperature of 340°C, a pressure of 3.5 MPa, the fuel consumption 2 h-1and a volume ratio of hydrogen/diesel - 300.
No.Chemical composition, wt.%Textural characteristicsCatalytic properties
Soo wt.%NiO wt.%Moo3wt.%R, wt.%Co(Ni)/Mo molarP/Mo molarSbeatsm2/g ∑cm3/gDcpAndDcf±15 E %Sulfur content, ppmXS,%Y%
340°370°340°
1the 4.7-16,2-1,75-1130,3512270200-24555-60295-32598,1

97,7
97
24,8-19,0-to 2.06-1040,359876210-23035-55295-31098,0

of 97.8
97
33,41,320,5-2,25-1160,3510568250-27045-70315-35097,6

97,5
98
44,6-21,31,22,40,261500,318550380-40085-90440-450 96,4

96,2
96
54,4-231,12,650,211140,3110855365-40060-70410-46596,6

96,2
96
65,5-21,10,432,000,091160,3110550280-370105-110340-37097,3

96,5
96
75,3-211,22,10,271440,4010840360-38065-90420-46096,6

96,4
96
Texture features derived from the adsorption isotherms of nitrogen: Sbeatsm2/g specific surface area by BET; Vcm3/g pore volume, desorption isotherms of nitrogen; Dcfthat Å average pore; Dcp±15 Å, % - proportion of pores with a size of Dcp±15 Å;

Catalytic characteristics: the content of sulfur in liquid petroleum products, ppm, when the above process temperatures; XS, % - degree wadrobes is eridania at 340° C; Y, % yield of liquid oil at 340°

1. The catalyst for processes of diesel hydrodesulphurization unit fractions, including an active component of the metal compounds VIII and VI groups, dispersed on a porous carrier, wherein the active component includes an integrated oxygen-containing compound of molybdenum and cobalt and/or Nickel in the following atomic ratio: Mo/(Co+Ni)of 1.5 to 2.5, the catalyst has a specific surface area of 100-190 m2/g, pore volume of 0.3-0.5 cm3/g, predominant pore 80-120 Å.

2. The catalyst according to claim 1, characterized in that as the carrier of the catalyst contains alumina or alumina with the addition of silica, or zeolite, or montmorillonite.

3. The catalyst according to claims 1 and 2, characterized in that as the active component contains, wt%: molybdenum oxide of Moo3in the amount of 14.0-29,0, cobalt oxide COO and/or Nickel oxide in the number of 3-8, medium of rest at a molar ratio Mo/(Co+Ni)of 1.5 to 2.5.

4. The method of preparation of the catalyst according to claim 1 for processes of diesel hydrodesulphurization unit fractions containing molybdenum oxide, cobalt oxide and/or Nickel oxide, a porous carrier comprising a carrier impregnated with a solution of a precursor of the active component, drying and heat treatment, characterized in that the application of the active component is carried out from the solution, containing complex metal compounds VIII and VI groups, stable mixture of complexing organic acids such as citric and lactic and/or malonic, acetic acid, formic acid, with a pH of 1.7 and 2.7.

5. The method according to claim 4, characterized in that as the carrier of the catalyst contains aluminum oxide, or aluminum oxide with the addition of silica, or zeolite, or montmorillonite.

6. The method according to claim 4, characterized in that the heat treatment of the impregnated carrier is carried out in a flow of nitrogen or air at a temperature not exceeding 200°C.

7. The way diesel hydrodesulphurization unit fractions, which includes the transmission diesel fraction through a layer of catalyst, characterized in that the use of the catalyst according to claims 1 to 3 or the catalyst prepared according to claims 4 to 6.

8. The method according to claim 7, characterized in that the process is carried out under the following conditions: partial hydrogen pressure of 3.5 MPa, temperature 300-370°C, the mass flow rate of fluid 2 h-1, the volumetric ratio of hydrogen/fuel 300.



 

Same patents:

FIELD: petroleum processing catalysts.

SUBSTANCE: invention relates to catalysts for production of low-sulfur motor fuels and methods for preparing such catalysts. Hydrodesulfurization catalyst according to invention is characterized by pore volume 0.3-0.7 mL/g, specific surface 200-350 m2/g, and average pore diameter 9-13 nm and containing following components, wt %: cobalt compounds (calculated as CoO) 2.5-7.5, molybdenum compounds (as MoO3), citric acid 15-35, boron compounds (as B2O3) 0.5-3.0, aluminum oxide - the rest, cobalt, molybdenum, citric acid, and boron optionally being part of complex compound having different stoichiometry. Catalyst is prepared by impregnating catalyst support with impregnation solution obtained by dissolving, in water or aqueous solution, following compounds: citric acid, ammonium paramolybdate (NH4)6Mo7O24·4H2O, at least one cobalt compound, and at least boron compound, addition order and component dissolution conditions being such as to provide formation of complex compounds, whereas concentration of components in solution is selected such that catalyst obtained after drying would contain components in above-indicated concentrations.

EFFECT: maximized activity of desired reactions ensuring production of diesel fuels with sulfur level below 50 ppm.

9 cl, 8 ex

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: proposed catalyst is composed of 12.0-25.0% MoO3, 3.3-6.5% CoO, 0.5-1.0% P2O5, and Al2O3 to the balance. Catalyst preparation comprises one- or two-step impregnation of support with solution obtained by mixing solutions of ammonium paramolybdate, cobalt nitrate, phosphoric and citric acids taken at ratios P/Mo = 0.06-0.15 and citric acid monohydrate/Co = 1±0.1, or mixing solutions of ammonium paramolybdate and phosphoric acid at ratio P/Mo 0.06-0.15 and cobalt acetate followed by drying and calcination stages. Diesel fraction hydrodesulfurization process is carried out in presence of above-defined catalyst at 340-360°C and H2-to-feedstock ratio = 500.

EFFECT: intensified diesel fraction desulfurization.

7 cl, 2 tbl, 13 ex

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: invention relates to catalysts for extensive hydrofining of hydrocarbon stock, in particular diesel fractions, to remove sulfur compounds. Catalyst of invention, intended for diesel fraction desulfurization processes, comprises active component, selected from oxides of group VIII and VIB metals and phosphorus, dispersed on alumina support, said alumina support containing 5-15% of montmorillonite, so that total composition of catalyst is as follows, wt %: molybdenum oxide MoO3 14.0-29.0, cobalt oxide CoO and/or nickel oxide 3-8, phosphorus 0.1-0.5, and support - the balance, molar ratio Mo/Co and/or Mo/Ni being 1.3-2.6 and P/Mo 0.08-0.1. Preparation of catalyst support consists in precipitation of aluminum hydroxide and addition of montmorillonite with moisture content 55-70% to water dispersion of aluminum hydroxide in amount such as to ensure 5-15% of montmorillonite in finished product, after which resulting mixture is extruded and extrudate is calcined at 500-600°C to give support characterized by specific surface 200-300 m2/g, pore volume 0.5-0.9 cm3/g, and prevailing pore radius 80-120 Å. Catalyst preparation comprises impregnation of calcined support with complex solution of group VIII and VIB metal salts and phosphorus followed by heat treatment in air or nitrogen flow at temperature not exceeding 200°C, impregnation solution notably containing molybdenum oxide and cobalt and/or nickel carbonate at Mo/Co and/or Mo/Ni molar ratio 1.3-2.6 stabilized with orthophosphoric acid and citric acid to P/Mo molar ratio between 0.008 and 0.1 at medium pH between 1.3 and 3.5. Described is also diesel fraction hydrodesulfurization process involving passage of diesel fraction through bed of above-defined catalyst.

EFFECT: intensified diesel fraction desulfurization.

9 cl, 3 tbl, 19 ex

FIELD: petroleum processing.

SUBSTANCE: object of invention is production of low-sulfur diesel fuels from high sulfur-level hydrocarbon feedstock. Proposed process consists in conversion of straight-run diesel fuel having high sulfur level in presence of preliminarily sulfidized heterogeneous catalyst containing group VIII metal and group VIB metal deposited on alumina characterized by pore volume 0.3-0.7 mL/g, specific surface area 200-350 m2/g, and average pore diameter 9-13 nm. Prior to be sulfidized, catalyst has following components: cobalt compounds in concentration 2.5-7.5% calculated as CoO; molybdenum compounds, 12-25% as MoO3; citric acid derivatives, 15-35% as citric acid; boron compounds, 0.5-3% as B2O3; and alumina, the balance. Process is conducted at 320-370°C, pressure 0.5-10 MPa, feedstock weight rate 0.5-5 h-1, and hydrogen-to-feedstock volume ratio 100-1000.

EFFECT: reduced sulfur level in diesel fuel to less than 50 ppm.

3 cl, 1 tbl, 8 ex

FIELD: petroleum processing.

SUBSTANCE: petroleum feedstock hydrocracking catalyst is prepared by compounding zeolite Y with aluminonickel(cobalt)-molybdenum(tungsten) oxide system. Specifically, low-alkalinity zeolite Y having silicate modulus 5.5-7.0 and crystallinity at least 70% is mixed with aluminum hydroxide having pseudoboehmite structure in proportion (1-9):1. Thus obtained mix is molded, dried, and calcined under water steam atmosphere to give molded thermally treated zeolite. The latter is impregnated with aqueous Ni(Co) and Mo(W) salt solutions or ground and compounded with aluminonickel(cobalt)-molybdenum(tungsten) oxide system by mixing with aluminum hydroxide and Ni(Co) and Mo(W) salts, after which follow molding and impregnation with aqueous Ni(Co) and Mo(W) salt solutions.

EFFECT: expanded catalyst preparation possibilities.

2 cl, 5 tbl, 4 ex

FIELD: petroleum processing.

SUBSTANCE: invention provides oil stock hydrotreatment catalyst containing alumina-supported hydrogenation components: cobalt, molybdenum, and tungsten in the form of oxides at weight ratio Co/Mo/W = 20:45:35 (15-25% in total), aluminum fluoride (10-30%), and promoter (2.5-16.5%): silicon oxide and/or rare-earth element oxides, in particular lanthanum oxide or lanthanum/cerium oxide mixture. Promoter may further contain up to 3% zirconium oxide. Alumina functions as binding material. Invention also covers oil stock hydrotreatment process, which is conducted in presence of claimed catalyst at 340-430°C, pressure 3-10 MPa, oil stock flow rate 0.5 to 3 h-1, and hydrogen-to-oil stock ratio 250 to 1000 nm3/m3. Catalyst is characterized by elevated hydrocracking and hydro-desulfurization activity and selectivity in oil stock hydrotreatment processes resulting in production of diesel distillates meeting European requirements (EN-590). Catalyst can be prepared on any existing catalyst preparation equipment.

EFFECT: simplified catalyst preparation technology and avoided formation of effluents.

5 cl, 3 tbl, 6 ex

FIELD: petroleum processing.

SUBSTANCE: invention, in particular, relates to petroleum fraction hydrofining process utilizing presulfided catalysts. Hydrofining process is described involving contacting petroleum fractions with presulfided catalyst containing alumina-carried cobalt, molybdenum, phosphorus, and boron, said process being conducted at 320-340°C, pressure 3.0-5.0 MPa, volumetric feed supply rate 1.0-6.0 h-1, normalized volumetric hydrogen-containing gas-to-feed ratio (500-1000):1 in presence of catalyst sulfided outside of reactor. Sulfidizing of catalyst is accomplished with hydrogen sulfide at 80-500°C and volumetric hydrogen sulfide flow rate 0.02-6.0 h-1. Chemical composition of catalyst is the following, wt %: MoS2 8.0-17.0, Co3S2 1.5-4.0, P2O3 2.5-5.0, B2O3 0.3-1.0, La2O3 1.0-5.0, and aluminum oxide - the balance.

EFFECT: simplified process.

2 cl, 1 tbl, 3 ex

FIELD: production of catalytic compositions.

SUBSTANCE: proposed method includes combining and bringing into interaction at least one component of non-precious metal of group VII and at least two components of metal of VIB group in presence of proton liquid; then composition thus obtained is separated and is dried; total amount of components of metals of group VIII and group VIB in terms of oxides is at least 50 mass-% of catalytic composition in dry mass. Molar ratio of metals of group VIB to non-precious metals of group VIII ranges from 10:1 to 1:10. Organic oxygen-containing additive is introduced before, during or after combining and bringing components into interaction; this additive contains at least one atom of carbon, one atom of hydrogen and one atom of oxygen in such amount that ratio of total amount of introduced additive to total amount of components of metals of group VIII to group VIB should be no less than 0.01. This method includes also hydraulic treatment of hydrocarbon material in presence of said catalytic composition.

EFFECT: enhanced efficiency.

29 cl, 8 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides petroleum fraction hydrofining catalyst with following chemical analysis, wt %: CoO 2.5-4.0, MoO3 8.0-12.0, Na20.01-0.08, La2O3 1.5-4.0, P2O5 2.0-5.0, B2O3 0.5-3.0, Al2O3 - the balance.

EFFECT: enhanced hydrofining efficiency in cases of feedstock containing elevated amount of unsaturated hydrocarbons.

2 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: catalytic system of hydrocarbon feedstock hydrofining is activated by circulating hydrogen-containing gas or mixture thereof with starting feedstock through layer-by-layer loaded catalysts in presulfided or in presulfided and oxide form at elevated temperature and pressure. Hydrogen is injected into circulating hydrogen-containing gas or mixture thereof with starting feedstock portionwise, starting concentration of hydrogen in circulating hydrogen-containing gas not exceeding 50 vol %. Starting feedstock consumption is effected stepwise: from no more than 40% of the working temperature to completely moistening catalytic system and then gradually raising feedstock consumption to working value at a hourly rate of 15-20% of the working value. Simultaneously, process temperature is raised gradually from ambient value to 300-340°C. Circulating factor of hydrogen-containing gas achieves 200-600 nm3/m3. Addition of each portion of hydrogen is performed after concentration of hydrogen in circulating hydrogen-containing gas drops to level of 2-10 vol % and circulation of hydrogen-containing gas through catalysts loaded into reactor begins at ambient temperature and further temperature is stepwise raised. Starting feedstock, which is straight-run gasoline or middle distillate fractions, begins being fed onto catalytic system at 80-120°C.

EFFECT: enabled prevention and/or suppression of overheating in catalyst bed.

5 cl, 6 tbl, 12 ex

FIELD: oxidation catalysts.

SUBSTANCE: invention concerns preparation of heterogeneous phthalocyanine catalyst for use in liquid-phase oxidation of sulfur-containing compounds and provides a method, which involves preparing nonwoven polypropylene carrier by treating it with boiling alkaline solution of sodium peroxycarbonate, 3.2-4.6 g/L, at pH 9-10 followed by treatment cobalt phthalocyanine-disulfonate, 3.2-4.6 g/L, and final treatment, which consists in washing preliminarily treated carrier with sodium hydroxide solution in concentration 0.1-0.5 g/L.

EFFECT: increased catalytic activity up to 92% and simplified catalyst preparation procedure.

2 cl, 1 tbl, 5 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention relates to catalysts for production of low-sulfur motor fuels and methods for preparing such catalysts. Hydrodesulfurization catalyst according to invention is characterized by pore volume 0.3-0.7 mL/g, specific surface 200-350 m2/g, and average pore diameter 9-13 nm and containing following components, wt %: cobalt compounds (calculated as CoO) 2.5-7.5, molybdenum compounds (as MoO3), citric acid 15-35, boron compounds (as B2O3) 0.5-3.0, aluminum oxide - the rest, cobalt, molybdenum, citric acid, and boron optionally being part of complex compound having different stoichiometry. Catalyst is prepared by impregnating catalyst support with impregnation solution obtained by dissolving, in water or aqueous solution, following compounds: citric acid, ammonium paramolybdate (NH4)6Mo7O24·4H2O, at least one cobalt compound, and at least boron compound, addition order and component dissolution conditions being such as to provide formation of complex compounds, whereas concentration of components in solution is selected such that catalyst obtained after drying would contain components in above-indicated concentrations.

EFFECT: maximized activity of desired reactions ensuring production of diesel fuels with sulfur level below 50 ppm.

9 cl, 8 ex

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: proposed catalyst is composed of 12.0-25.0% MoO3, 3.3-6.5% CoO, 0.5-1.0% P2O5, and Al2O3 to the balance. Catalyst preparation comprises one- or two-step impregnation of support with solution obtained by mixing solutions of ammonium paramolybdate, cobalt nitrate, phosphoric and citric acids taken at ratios P/Mo = 0.06-0.15 and citric acid monohydrate/Co = 1±0.1, or mixing solutions of ammonium paramolybdate and phosphoric acid at ratio P/Mo 0.06-0.15 and cobalt acetate followed by drying and calcination stages. Diesel fraction hydrodesulfurization process is carried out in presence of above-defined catalyst at 340-360°C and H2-to-feedstock ratio = 500.

EFFECT: intensified diesel fraction desulfurization.

7 cl, 2 tbl, 13 ex

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: invention relates to catalysts for extensive hydrofining of hydrocarbon stock, in particular diesel fractions, to remove sulfur compounds. Catalyst of invention, intended for diesel fraction desulfurization processes, comprises active component, selected from oxides of group VIII and VIB metals and phosphorus, dispersed on alumina support, said alumina support containing 5-15% of montmorillonite, so that total composition of catalyst is as follows, wt %: molybdenum oxide MoO3 14.0-29.0, cobalt oxide CoO and/or nickel oxide 3-8, phosphorus 0.1-0.5, and support - the balance, molar ratio Mo/Co and/or Mo/Ni being 1.3-2.6 and P/Mo 0.08-0.1. Preparation of catalyst support consists in precipitation of aluminum hydroxide and addition of montmorillonite with moisture content 55-70% to water dispersion of aluminum hydroxide in amount such as to ensure 5-15% of montmorillonite in finished product, after which resulting mixture is extruded and extrudate is calcined at 500-600°C to give support characterized by specific surface 200-300 m2/g, pore volume 0.5-0.9 cm3/g, and prevailing pore radius 80-120 Å. Catalyst preparation comprises impregnation of calcined support with complex solution of group VIII and VIB metal salts and phosphorus followed by heat treatment in air or nitrogen flow at temperature not exceeding 200°C, impregnation solution notably containing molybdenum oxide and cobalt and/or nickel carbonate at Mo/Co and/or Mo/Ni molar ratio 1.3-2.6 stabilized with orthophosphoric acid and citric acid to P/Mo molar ratio between 0.008 and 0.1 at medium pH between 1.3 and 3.5. Described is also diesel fraction hydrodesulfurization process involving passage of diesel fraction through bed of above-defined catalyst.

EFFECT: intensified diesel fraction desulfurization.

9 cl, 3 tbl, 19 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention relates to catalysts for deep hydrofining of hydrocarbon feedstock, in particular diesel fractions, to remove sulfur compounds. Invention, in particular, provides catalyst for hydrodesulfurization of diesel fractions including active component selected from group VIII and VIB metal oxides dispersed on alumina carrier, which is, in particular, composed of aluminum oxides, 85-95%, and H form or cation-substituted form of zeolite ZSM-5, mordenite, zeolite BEA, or zeolite Y, 5-15%. Active component is selected from oxides of molybdenum and cobalt and/or nickel. Carrier preparation method comprises precipitation of aluminum hydroxide, incorporation of zeolite in H form or cation-substituted form in amount 5-15% (based on final product) and peptizing agent into aluminum hydroxide powder, extrusion of resulting mixture, drying, and calcination at 450-600°C. Preparation of catalyst includes impregnation of above-defined carrier with complex solution of group VIII and VI metal salts in air or nitrogen flow at temperature not higher than 200°C. Diesel fraction hydrodesulfurization process is also described.

EFFECT: enhanced purification of diesel fractions.

10 cl, 2 tbl, 14 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to a method of preparing ethylene oxide production catalyst containing silver deposited on alumina carrier originally having sodium and silicate ions on its surface. Carrier is preliminarily treated with aqueous solution of lithium salt at temperature below 100°C, after which at least 25% sodium ions are removed and replaced with up to 10 mln-1 lithium ions. Carrier is dried and then silver and promoters are precipitated on the pretreated and dried carrier.

EFFECT: achieved stability of catalyst.

7 cl, 11 tbl, 17 ex

FIELD: gas treatment catalysts.

SUBSTANCE: invention concerns environmental protection area and aims at neutralizing toxic components of emission gases and, more specifically, related to a method of preparing catalyst for oxidative treatment of gases polluted by hydrocarbons and carbon monoxide. Invention provides catalyst supported by stainless steel containing 0.05-0.15 wt % ruthenium or ruthenium in the same quantity combined with platinum or palladium in quantity not exceeding 0.05 wt %. Catalyst preparation method is also described.

EFFECT: increased degree of removal of hydrocarbons, increased strength of catalyst, and reduced price of catalyst.

2 cl, 2 tbl

FIELD: petroleum processing.

SUBSTANCE: petroleum feedstock hydrocracking catalyst is prepared by compounding zeolite Y with aluminonickel(cobalt)-molybdenum(tungsten) oxide system. Specifically, low-alkalinity zeolite Y having silicate modulus 5.5-7.0 and crystallinity at least 70% is mixed with aluminum hydroxide having pseudoboehmite structure in proportion (1-9):1. Thus obtained mix is molded, dried, and calcined under water steam atmosphere to give molded thermally treated zeolite. The latter is impregnated with aqueous Ni(Co) and Mo(W) salt solutions or ground and compounded with aluminonickel(cobalt)-molybdenum(tungsten) oxide system by mixing with aluminum hydroxide and Ni(Co) and Mo(W) salts, after which follow molding and impregnation with aqueous Ni(Co) and Mo(W) salt solutions.

EFFECT: expanded catalyst preparation possibilities.

2 cl, 5 tbl, 4 ex

FIELD: chemical industry; petrochemical industry; other industries; methods of production of the catalysts of hydrogenation of arenes.

SUBSTANCE: the invention is pertaining to the field of the catalytic chemistry, in particular, to production of the catalysts used for dearomatization of the diesel fractions. The invention presents the catalyst for hydrogenation of the arenas containing platinum the carrier, which aluminum oxide containing of no more than 500 ppm of impurities in the mixture with the crystalline mesosculiferous aluminosilicate with the molar ratio of Si/Al equal to 10-60 at the following contents of the ingredients (in mass %): platinum (Pt) - 0.15-0.60; aluminum oxide (AI2O3) - 59.85-94.4; crystalline mesoosculiferous aluminosilicate (AlxSiyOz) - 5-40, where х = 0.017 - 0.1; y = 1; z = 2.026 - 2.15. The invention also presents the method of preparation of the catalyst of hydrogenation of the arenes providing for production of the carrier, deposition of platinum on the carrier by the method of the competitive impregnation from the combined solution of the carrier from the joint solution of the chloroplatinic acid, acetic acid and hydrochloric acid the subsequent drying, and burning, differing that the carrier is produced by mixing of the powdery aluminum oxide containing of no more than 500 ppm of the impurities, and the crystalline mesoosculiferous aluminosilicate AlxSiyOz, (where х = 0.017 - 0.1; y = 1; z = 2.026 - 2.15), with the molar ratio molar ratio of Si/Al equal to 10-60, humidification of the produced mixture and the jellification by the 1.5 - 5 % solution of the nitric acid. The technical result of the invention is the increased hydrogenating activity of the catalyst.

EFFECT: the invention ensures the increased hydrogenating activity of the catalyst.

3 cl, 2 tbl, 4 ex

FIELD: chemical industry; other industries; methods of production of the platinum catalysts.

SUBSTANCE: the invention is pertaining to the method of production of the platinum catalyst used for purification of the exhaust gases of the internal combustion engines. The invention presents the description of the method of manufacture of the catalyst for purification of the exhaust gases of the internal combustion engines including deposition of the aluminum oxide layer containing the catalytically active component - platinum on the inert steel carrier containing 15-23 % of chromium and 4.5-5.1 % of aluminum, with the subsequent drying and calcinations. At that before deposition of the aluminum oxide layer containing the catalytically active component - platinum the inert steel carrier is subjected to etching in the hydrochloric acid diluted with the water in the ratio of 1:1 within 25-35 seconds at the temperature of 20-25°С with the subsequent washing by the running and distilled water and the further heat treatment in the air at the temperature within the interval of 850-950°С for 10-20 hours, then it is subjected to the treatment with the ultrasound with the frequency of 18 kHz within 1-2 minutes and with the subsequent treatment of the surface of the inert steel carrier in the KOH alkaline solution with concentration of 10 % within 30-60 minutes for transformation of the oxides of the surface layer into the hydroxides. The technical result of the invention is simplification of the production process.

EFFECT: the invention ensures simplification of the production process.

3 cl

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: invention relates to catalysts for extensive hydrofining of hydrocarbon stock, in particular diesel fractions, to remove sulfur compounds. Catalyst of invention, intended for diesel fraction desulfurization processes, comprises active component, selected from oxides of group VIII and VIB metals and phosphorus, dispersed on alumina support, said alumina support containing 5-15% of montmorillonite, so that total composition of catalyst is as follows, wt %: molybdenum oxide MoO3 14.0-29.0, cobalt oxide CoO and/or nickel oxide 3-8, phosphorus 0.1-0.5, and support - the balance, molar ratio Mo/Co and/or Mo/Ni being 1.3-2.6 and P/Mo 0.08-0.1. Preparation of catalyst support consists in precipitation of aluminum hydroxide and addition of montmorillonite with moisture content 55-70% to water dispersion of aluminum hydroxide in amount such as to ensure 5-15% of montmorillonite in finished product, after which resulting mixture is extruded and extrudate is calcined at 500-600°C to give support characterized by specific surface 200-300 m2/g, pore volume 0.5-0.9 cm3/g, and prevailing pore radius 80-120 Å. Catalyst preparation comprises impregnation of calcined support with complex solution of group VIII and VIB metal salts and phosphorus followed by heat treatment in air or nitrogen flow at temperature not exceeding 200°C, impregnation solution notably containing molybdenum oxide and cobalt and/or nickel carbonate at Mo/Co and/or Mo/Ni molar ratio 1.3-2.6 stabilized with orthophosphoric acid and citric acid to P/Mo molar ratio between 0.008 and 0.1 at medium pH between 1.3 and 3.5. Described is also diesel fraction hydrodesulfurization process involving passage of diesel fraction through bed of above-defined catalyst.

EFFECT: intensified diesel fraction desulfurization.

9 cl, 3 tbl, 19 ex

Up!