Catalyst, carrier preparation method, catalyst preparation method, and diesel fraction hydrodesulfurization process

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

 

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 catalysts for Hydrotreating diesel fractions from sulfur compounds contain catalytically active compounds of molybdenum and/or tungsten and cobalt and/or Nickel is deposited on the surface of an inert porous carrier, oxide or sulfide form.

The known method of obtaining catalysts for hydrodesulphurization unit containing dispersed aluminum oxide compounds Co(Ni)-Mo(W)is extrusion catalytically active mass with subsequent stages of drying, heat treatment and pre-activation by solifidianism. In this case, the active ingredient is added to the aluminum hydroxide with bemani or pseudoboehmite structure (EN 2137541, B01J 23/88, 20.09.99; 2074025, B01J 21/04, 27.02.97). As precursors of the active component using a water-soluble salt of molybdenum or tungsten, mainly ammonium molybdate and cobalt or Nickel, on the main nitrate (RU 2137541, B01J 23/88, 20.09.99) or a complex metal salt solution VIII and VI groups, stabilized with phosphoric acid at pH 0.5-2.5 (RU 2074025, B01J 21/04, 27.02.97). The main disadvantage of this method is its low gidroobesserivaniya activity that does not allow you to get low-sulfur diesel fuel with sulfur content less than 300 ppm). A big disadvantage of these catalysts is also low mechanical strength, which is a significant limitation for the operation of the catalyst under the conditions of Hydrotreating.

Another known method of producing catalysts for hydrodesulphurization unit containing dispersed on the surface of the carrier compounds of Co(Ni)-Mo(W)is a method of impregnation of the inert carrier with solutions of compounds of the precursors of the active component with the subsequent stages of drying, calcination and sulfatirovnie. As a porous inert media typically use calcined extrudates based on aluminium oxide and/or silicon oxide. To regulate acid-base properties of the media modifying additives ultrastable (with respect zeolite Y (5-7 wt%), oxides of titanium, zirconium and amorphous aluminosilicates, as well as additives of oxides of phosphorus, boron and others. For the preparation of catalysts gidromassazhnye diesel fractions, it is recommended to use calcined media is within specific surface area of 200-300 m 2/g, pore volume of 0.5-0.9 cm3/g and an apparent density of 0.5-0.8 g/cm3in this case, after the application of Co(Ni)-Mo(W) of the active component and annealing the specific surface area of the catalyst will vary within 150-275 m2/g, pore volume of 0.4 - 0.8 cm3/g and an apparent density of 0.5 - 1.0 g/cm3(US 3840472, B01J 27/19, C10G 45/08, 8.10.74). The catalyst is usually in the form of cylinders or trilistniku size 1/8, 1/16 or 1/32 of an inch. In some of the patents discussed the optimal distribution of the pore sizes, providing the highest activity in the oil hydrodesulphurization unit fractions. In particular, for the purification of diesel fractions requires a narrow distribution of pore size, pore diameter 70-130 Å must be at least 75% of the total pore volume (US 4818743, B01J 23/85, 04.04.89; 4879265, B01J 23/24, 07.11.89), a fraction of the volume of pores of diameter greater than 130 Å must not exceed 10% (US 4818743). This distribution of pore size not only provides high availability of sulfur compounds to the surface of the active component, but reduces the possibility of coking time.

The application of active component is carried out as a sequential impregnation of the individual solutions, and a single impregnation of joint solutions. For preparation of the impregnating solutions typically use the oxides of tungsten and molybdenum, ammonium molybdate salt is Oh and tungstic 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 (mainly molybdenum oxide and ammonium molybdate) and sustainability joint impregnating solutions containing compounds VIII and VI groups is the use of concentrated aqueous solutions of ammonia. As compounds precursors of cobalt and Nickel are used as water-soluble and poorly soluble compounds, most often it is a nitrate, sulfat, acetate, citrate, carbonate, hydroxide and oxide of cobalt and/or Nickel. The main disadvantage of joint impregnating solutions containing compounds VIII and VI groups, is their low stability in the presence of an excess of phosphoric acid, the nitrate anion (NO3-) and ammonium cation due to the formation and precipitation of phosphate of cobalt (Nickel) and ammonium.

Known bimetallic Co-Mo and Ni-Mo catalysts containing 8-10 wt.% Moo3and 3 wt.% Soo, deposited on 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 fuel 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 petroleum fractions.

One way to achieve deep hydrodesulphurization unit diesel fractions is to increase the pressure and temperature of the process that allows 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 due to coking of the catalyst surface hydrocarbon components of diesel fuel. The disadvantage of this met the da is also increasing kekirawa activity of Co(Ni)-Mo(W) catalysts at elevated temperatures, that inevitably leads to a decrease of the yield of liquid petroleum products and lower cetane number of diesel fuel.

Another way to achieve a deep level of cleaning 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 must use the media with well-developed porous structure and a 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 4818743, 4879265, 2003/0173256). 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). To ensure uniform distribution of the high content of activehotels by media (up to 6 atoms of Mo on nm 2Al2About3helps optimize the pH and composition of the impregnating solutions by introducing acidic molybdenum-containing additives in the fluids (N3PO4N3IN3and other [US 3755196, 4392985, 4879265]. For the formation of the "CoMoS II centers must also exclude education cristallizing phases Co3O4and CoAl2About4at the stage of impregnation and heat treatment, since the latter when the pretreatment of the catalyst in structuresa environment (sulfatirovaniu) is converted into sulphide of cobalt, Co9S8inactive in the reaction hydrodesulphurization unit. Education cristallizing phases Co3O4and CoAl2O4reduced with the introduction of organic additives, such as citric acid (US 2003/0173256; 2006/0054536), prokalivaem active complex at temperatures above 300° (US 2003/0173256; 2006/0054536) and by sulfatirovnie catalyst in soft conditions (US 4879265; 2003/0173256).

Remove β-dialkyldimethyl can be performed through a preliminary transformation into more reactive compounds routes: hydrogenation of one of the benzene rings, isomerization (transfer of alkilnykh groups of βposition γ-), dealkylation (delete one of the alkyl groups), rupture of the C-C bond thiophene rings. The course of these reactions is usually achieved for o(Ni)-Mo(W) catalysts by increasing the acidic properties of alumina carriers due to their modification additives of titanium oxide, zirconium and silicon additives amorphous aluminosilicates and zeolites, as well as anions of phosphoric and/or boric acid. Transformation β-dialkyldimethyl in reactive derivatives can also be achieved by modification of the active component additives that increase its moisturizing ability, additives such as Ni, Cu or metals Pt-th group (Pt, Pd, Rh).

Thus, the deep cleaning of diesel fuels from sulfur compounds can provide Co(Ni)-Mo(W) catalysts with high catalytic activity in the reactions of transformation of sulfur compounds and resistance to decontamination of sulfur compounds and hydrogen sulfide formed by the reaction of hydrogenolysis. Along with the activity and stability in the reactions of transformation of sulfur compounds, the catalysts must ensure that the resulting diesel fuel required cetane number, distribution fractions according to boiling points, density, content of aromatic and polyaromatic compounds. To solve these problems offers a variety of technological solutions, in particular the variation of the type and structure of media, composition and quantity of the modifying additives of the composition and quantity of the active component, method of its application to the media.

Known catalyst hydrodesulphurization unit of hydrocarbon who Iria, includes metal VI and/or VIII gr, deposited on a refractory inorganic substance selected from the group comprising alumina, a mixture of aluminum oxide and silicon oxide and/or magnesium oxide and/or calcium oxide and/or zeolite, and/or zinc oxide, and, if necessary, the boron compound (US 5686374, B01J 29/10, 11.11.97). The catalyst shows high activity in reactions hydrodesulphurization unit has a longer service life, however, has a high activity in reactions of cracking.

The patent (US 6267874, B01J 21/12, 31.07.2001) describes a Hydrotreating catalyst, which uses mixed oxide aluminum-silicon carrier and an active component based on the items VIII (Co, Ni, Ru, Rh, Pd, It, Pt) and/or VI (Mo, W) group of the periodic table. In the composition of the medium can be introduced additives of titanium oxide, Zirconia, zeolite, clay. The main distinctive property of the medium is high dispersion of silicon oxide and pentecosta acidity, not less than 50 μmol/g For impregnation is used ammonia solution to pH 9, containing Nickel nitrate, paramolybdate ammonia and citric acid. The catalyst is characterized by high resistance to deactivation by hydrogen sulfide, high activity in the hydrodesulphurization unit and displays considerable efficiency in the process of deep hydrodesulphurization unit sour hydrocarbon topl the century The catalyst shows high efficiency hydrocracking, hydrodearomatization, hydroisomerization. However, in the patent serves expensive technology synthesis kremniikarbidnoi media, in particular the use as precursors of alkoxides of silicon and aluminum or high temperatures (40-90° (C) for carrying out the stages of co-precipitation and aging of gels in the case of using inorganic compounds of silicon and aluminum.

A known method of preparation of Co(Ni)-Mo(W) catalysts for the desulfurization of petroleum fractions, including extrusion and heat treatment of the medium on the basis of oxides of aluminum, boron, titanium or zirconium, manganese (Al2O3:In2O3:TiO2(ZrO2):MnO2= 1:0.005-0.053:0.002-0.042:0.0004-0.016), impregnation of ammonium solution containing ammonium molybdate(tungsten)acid and cobalt(Nickel) nitric acid followed by heat treatment at 530°WITH (EN 2155637, B01J 23/88, 10.09.2000). The main disadvantage of the catalyst is its lack of activity, which does not allow to use it for deep hydrodesulphurization unit of crude oil. The catalyst contains, wt%: 10-15 Moo3and 4-6 Soo, provided the diesel hydrodesulphurization unit fractions on the level 93.3-93.5% when the sulfur content of 0.72 wt.%, a pressure of 3 MPa, 380°C, space velocity of the raw materials 2.5 h-1the ratio of the circulation of the hydrogen-containing gas of 400 nm 3/m3of raw materials.

There is a method of preparation of the catalyst by impregnation of a pre-calcined carrier with a solution of heptamolybdate ammonium in the first phase or solution of active metals on the second intermediate outputs and final heat treatments including drying and calcining, at the second stage impregnation of the carrier use a solution of nitrate of cobalt and/or Nickel nitrate and intermediate heat treatment is carried out at a temperature of 100-200°and the final heat treatment comprising drying and calcining, carried out respectively at a temperature of 100-200°and amounts to 400-650°WITH (EN 2246987, B01J 37/02, 27.02.2005).

In the patent (US 3840472, B01J 11/06, 8.10.1974) proposes to prepare an impregnating solution to use molybdenum oxide and one of the metals of group VIII of the periodic system, which is used in the form of carbonate, hydroxide, acetate, formate or oxide in solid form, dissolving them in phosphoric acid at the following concentrations of 0.3-2.5 mol/l, R, 0.4-1.5 mol/l of a metal of group VIII and 1-3 mol/l Mo.

Approximate methods for the preparation of the catalyst is available in a number of patents the company Union Oil Company of California: US 4500424, B01J 027/185, 19.02.1985; 4818743, B01J 027/185, 4.04.1989 and other 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, the e less wt.%: 17-25 of Moo3, 1-6 COO or NiO 1-4 and P, provided that the molar ratio P/Moo3in the solution above 0,1, mostly 0.2 and pH in the range 0-1,0. The patent also States that in the case of paramolybdate ammonium, as a precursor of the metal of group VIII is better to use nitrate of cobalt or Nickel. In the case of molybdenum oxide as the precursor of the metal of group VIII is better to use carbonate of cobalt or Nickel.

In a number of patents Union Oil Company of California: US 3755150; 3755196, 28.08.1973; 4846961, 11.07.1989, describes the catalyst is obtained by impregnation of alumina-modified silica, a salt solution 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 (or 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 pairs of the molybdate of ammonium and nitrate cobalt (or 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. An impregnating solution was stable, provided the content is not less than 17 wt.% Moo3and the mass ratio of COO/Moo3in the range of 0.1-0.4.

The main disadvantage of the catalysts described in patents US 3755150, 3755196, 4392985, 4846961, is the high content of phosphorus in the catalyst (2.4 to 3.5 wt.% R), which leads to insufficient high activity in the process for hydrotreatment of diesel fractions in the processing of sour crude oils and to a high enough coxworthy.

In the patent US 4879265, B01J 027/19, 7.07.1989 described method of preparation of a highly active catalyst which contains, in wt.%: 17-27 of Moo3, 1-4 R and 0.5-5 NiO. The catalyst is prepared by impregnation with a solution containing 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 (or Nickel), but note that it is possible to use oxide of molybdenum and an oxide or carbonate of cobalt (or Nickel). During annealing the catalyst for the most part citric acid is decomposed remains n is more than 0.5 wt.% C. The catalyst has high activity in the processes hydrodesulphurization unit and Hydrotreating.

Closest to the technical nature of the claimed and achieved result is the catalyst described in the application US 2006/00545536, 16.03.2006. The catalyst of the prototype is prepared by impregnating alumina carrier containing 1 wt.% silicon dioxide or 5 wt.% ultrastabilized of zeolite Y, an aqueous solution containing cobalt citrate, phosphoric acid (85%solution) and molybdophosphoric acid, provided that the pH of the solution in the range of 0.52, with first, followed by drying in a stream of nitrogen and then in air stream at 120°C for 12 hours, After annealing at 120°the catalyst contains, wt%: 10-40 NGO3mainly 26-29, 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 silicon dioxide (99/1) or γ-Al2About3with zeolite Y (95/5). The catalyst has high gidroobesserivaniya activity, providing a residual sulfur content at the level of 8-10 ppm at a pressure of 4.9 MPa, space velocity of 1.5 h-1, the ratio of hydrogen/feedstock 200 m3/m3and a temperature of 350°and sulfur in the raw materials of 1.61 wt.%.

The main disadvantage of this catalyst is high with the actual content of phosphorus, that leads to quite a 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 in the processing of sour crude oils at low partial pressure of hydrogen.

The problem solved by the invention: development of the composition and method of preparation of active and stable catalyst containing compounds of molybdenum and cobalt and/or Nickel dispersed on the surface of the modified alumina carrier, and intended for carrying out processes of hydrodesulphurization unit sour diesel fractions on existing hydrotreatment units.

This is achieved by optimization of the texture and composition of the catalyst containing compounds of molybdenum and cobalt (Nickel)dispersed on the surface of the modified alumina carrier, as well as the optimization of the acid-base properties.

Optimization of texture and acid-base properties of the medium is achieved by the fact that as the carrier of the calcined catalyst contains alumina, modified additives powders zeolite in the H form or cation-exchanged form. Introduction into the molding composition on the basis of aluminum hydroxide, poluchennogo is one of the deposition methods (continuous or periodic) or by hydrolysis of aluminum isopropylate, powders zeolite with a particle size of 2-10 μm can provide a high specific surface of the carrier (not below 250 m2/g), a well-developed porous structure (not less than 0.6 cm3/g) with a narrow distribution of the pore size (mainly with pores 80-140 Å), the optimal acidity.

The presence of media additives zeolite helps to increase the acidity of the medium in comparison with the aluminum oxide and the formation of highly dispersed compounds of molybdenum and promoter (Co or Ni), which allows a high catalytic activity in the reaction hydrodesulphurization unit. In addition, the increasing acidity of the medium due to the introduction of zeolites ZSM-5, mordenite, WEAH or Y has a positive effect on the stability of the catalyst to deactivation by hydrogen sulfide formed by the reaction of the hydrogenolysis of C-S communication sulfur aromatic compounds. Introduction to media zeolites in the H form and the cation-exchanged form, and especially in the case of cations, Ni and Co, promotes hydrogenation ability of the catalyst hydrodesulphurization unit and, therefore, facilitates β-dialkyldimethyl in reactive derivative along the routes of the hydrogenation of one of the benzene rings and isomerization (transfer of alkilnykh groups of βposition γ-).

Optimization of the composition of the active complex and its evenly the application is achieved by the content of compounds of molybdenum is mainly within 16-22 wt.% Moo3and the ratio of Mo/(Co+Ni) varies in the range of 1.5 to 2.5, which is sufficient to ensure high activity in the reaction of diesel hydrodesulphurization unit fractions. When the specified content of Moo3and the ratio of Mo/is formed With an optimum content of the "CoMoS II centers containing cations of cobalt or Nickel in a layered structure MoS2. To increase the uniformity of application of the active complex uses impregnating solutions containing molybdenum oxide and carbonate cobalt (Nickel), stable additives phosphoric acid and citric acid. If the pH of impregnating solutions in the range of 1-2,5 and the atomic ratio of P/Mo predominantly in the range of 0.08 to 0.15 is sufficient to ensure the stability of the impregnating solutions for 3-4 months. Introduction in the impregnating solution of the additive citric acid at a molar ratio Coco3/citric acid equal to 3/2, eliminates the interaction of compounds of cobalt with aluminum oxide in the stages of impregnation and education cristallizing phases Co3O4and CoAl2O4during annealing. The lack of Co3O4and CoAl2O4recorded according to the electronic spectroscopy.

In addition, slow susceptometer media in a stream of inert gas or air atmosphere allows you to avoid crystallization of the active complex, and calcining in a stream of air at temperatures up to 240°excludes active destruction complex. These techniques, used for the preparation of the catalyst, provide formation of a large number of "CoMoS II centers and increase the activity of the catalyst at moderate temperatures of diesel hydrodesulphurization unit fractions.

In addition, the reduction of the content of phosphate ion in the catalyst to the ratio 0,08-0,1 ensures its resistance to deactivation as a result of sediment hydrocarbon components of diesel fuel on the catalyst surface. At the specified ratio P/Mo eliminates the surface modification of alumina carrier phosphate ions.

The media, and hence the catalyst is predominantly made in the form of extrudates - cylinder or 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 diesel hydrodesulphurization unit fractions.

The above method of preparation of the proposed catalyst can increase the activity of Co(Ni)-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 300-500 m3/m3raw materials and the stability of the catalyst to deactivation in prisutstvie the organic serosoderjaschei compounds at elevated temperatures, therefore, to use 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.

The process for hydrotreatment of diesel fractions in existing industrial installations carried out at a temperature 340-400°C, at a 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 hydrogen-containing gas 250-350 m3/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), to the which 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 minutes 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.

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 500. At the moment when the costs of reagents stabilized, begin heating the reactor from room temperature to 350°With that Khujand who are within 35-40 minutes The process is carried out at a temperature of 350°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 components. 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.

In some experiments the definition of AK is Yunosti catalysts is carried out at a temperature of - 340°C, a pressure of 3.5 MPa, the flow rate of the liquid fuel 2 h-1and the ratio of hydrogen/feedstock - 300, conditions modificirovanie similar to those described above. 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 the following examples.

Example 1 (table 1).

For modifying alumina media use mordenite powder NaH-MOR: atomic ratio Si/Al - 6, the sodium content is 0.15 wt.%, specific surface area of 400 m2/g, micropore volume - 0,18 cm3/g, the proportion of particles of size less than 9.5 μm is 90%.

To 80 g of aluminum hydroxide obtained by the method of periodic deposition, containing 95% of pseudoboehmite and having a humidity of 75%, type of 3.97 g of mordenite powder NaH-MOR, having a moisture content of 11%, and 0.2 ml of a 7%nitric acid, stirred Z-shaped mixer for 20 minutes. The resulting mass is formed into extrudates through a die plate with a diameter of 1.6 mm extrudates calcined in air flow at 550°C for 4 hours After calcination of the extrudates from the may contain the γ -Al2About3and NaH-MOR mass ratio of 85/15, have a capacity of 0.75 cm3/g, a specific surface area of 320 m2/g, pore volume of 0.62 cm3/g and average pore 82 Å (isotherms of nitrogen adsorption).

For preparation of the impregnating solution to 7,09 g of cobalt carbonate add 42 ml of distilled water and heated to a temperature of 80°C. is Then added with stirring in portions to 8.34 g of citric acid monohydrate, while there has been intense emission of CO2. Waiting for the complete dissolution of the precipitate, add to 20.5 g of molybdenum oxide Moo3and 3.28 g of phosphoric acid (85%solution). Continue to stir the solution at a temperature of 80°until dissolved. After dissolution, the solution volume is 50 ml of a Solution containing 29 wt.% Moo3, characterized by a molar ratio Mo/ - 2.2 and P/Mo 0,2, has a pH of 1.25.

To 30 g of the calcined extrudates add 22.5 ml of impregnating solution, and incubated for 15 minutes. The impregnated extrudates are dried in a stream of nitrogen and then in the muffle in an atmosphere of air at 200°C for 10 hours

The catalyst contains, wt%: 21.3 molybdenum oxide (hereinafter, based on Moo3), 4.8 cobalt oxide (hereinafter, based on COO) and 0.71 phosphorus (calculated as P), the ratio of Mo/Co according to the chemical analysis is 2.3, P/Mo 0,15.

The catalyst for the settlement of the s annealing at 200° With has a specific surface area (Sbeats) - 105 m2/g, pore volume (VΣ) - 0,24 cm3/g and the average radius of the pores (Dcp) - 99 Åcharacterized p.p. 12400-14000 cm-1and 14200-18500 cm-1in the electronic spectra of diffuse reflection.

Of the extrudates of catalyst prepared fraction size 0.2-0.5 mm, 2 g fraction is loaded into the reactor and subjected to solifidian in the stream of hydrogen sulfide at 400°C for 2 h to Determine the yield of liquid oil and sulfur contents, which provides sulpicianus catalyst feeding him straight-run diesel fuel with a sulfur content equal to 1.06 wt.%, and the following process conditions: temperature 350°C, pressure of 3.5 MPa, mass flow rate of diesel fuel 2 h-1and a volume ratio of hydrogen/diesel fuel 500.

Under these conditions, the process for hydrotreatment of diesel fuel catalyst enables the reduction of sulfur in liquid petroleum products to the level 26-31 ppm and the yield of liquid oil products at the level of 96-98%.

Example 2 (table 1).

Similar to example 1, except for preparing media to aluminum hydroxide (80 g) add 3,68 g of powder of zeolite H-ZSM-5. The zeolite powder has a moisture content of 4%, the atomic ratio Si/Al - 17, a specific surface area of 385 m2/g, micropore volume of 0.2 cm3/g, the proportion of particles less than 10 microns costal is no 90%.

The calcined carrier contains γ-Al2O3and H-ZSM-5 in a weight ratio of 85/15 and has the following characteristics: moisture 0,80 cm3/g, specific surface area 300 m2/g, pore volume of 0.57 cm3/g and average pore 80 Å.

The composition and textural characteristics of the catalyst are shown in table 1. The ratio of Mo/Co catalyst is 2.1, R/Mo - 0,18.

Under the conditions of test example 1, the catalyst provides a 92% yield of liquid oil and the sulfur content in them at the level 65-80 ppm.

Example 3 (table 1).

Similar to example 1, except for preparing media to aluminum hydroxide (80 g) type of 3.60 g of a powder of zeolite BEA. The zeolite powder has a moisture content of 2%, the atomic ratio Si/Al - 12, specific surface area of 600 m2/g, micropore volume is 0.27 cm2/g, the proportion of particles less than 7.5 μm is 90%.

The calcined carrier containsγ-Al2About3and H-BEA mass ratio of 85/15 and has the following characteristics: moisture capacity of 0.87 cm3/g, a specific surface area of 355 m2/g, pore volume of 0.66 cm3/g and average pore 80 Å.

The composition and textural characteristics of the catalyst are shown in table 1. The ratio of Mo/Co catalyst is 2.25, P/Mo - 0,10.

Under the conditions of test example 1, the catalyst provides 96-98% yield of liquid oil is of Reducto and sulfur content in them at the level of 155-165 ppm.

Example 4 (table 1).

Similar to example 1, except for preparing media to aluminum hydroxide (80 g) add 4,47 g of zeolite powder HNaY. The zeolite powder has a moisture content of 20%, the atomic ratio Si/Al - 2,3, specific surface 515 m2/g, micropore volume - 0,23 cm3/g, the proportion of particles less than 50 μm is 90%.

The calcined carrier contains γ-Al2O3and HNaY mass ratio of 85/15, and has the following characteristics: moisture 0,88 cm3/g, a specific surface area of 330 m2/g, pore volume of 0.66 cm3/g and average pore 85 Å.

The composition and textural characteristics of the catalyst are shown in table 1. The ratio of Mo/Co catalyst is 2.4, P/Mo 0,15.

Under the conditions of test example 1, the catalyst provides 95-96% yield of liquid oil and the sulfur content in them at the level of 230 to 250 ppm.

Example 5 (table 1).

Similar to example 2, to prepare an impregnating solution using 9,67 g of cobalt carbonate, 2.4 g of Nickel carbonate, 14,21 g of citric acid monohydrate, 29,23 g of molybdenum oxide and 3.51 g of phosphoric acid (85%solution). After complete dissolution the solution contains 35 wt.% Moo3, characterized by a molar ratio Mo/(Co+Ni) - 2.0 and P/Mo 0,15 has a pH of 1.70.

The composition and textural characteristics of the catalyst are shown in table 1. The ratio is s Mo/(Co+Ni) in the catalyst is 2.0 and P/Mo 0,12.

Under the conditions of test example 1, the catalyst provides a 95% yield of liquid oil and the sulfur content in them at the level of 120-130 ppm.

Example 6 (table 1).

Similar to example 2, to prepare an impregnating solution used to 7.67 g of cobalt carbonate, 9,03 g of citric acid monohydrate, 13,94 g of molybdenum oxide and 0.9 grams of phosphoric acid (85%solution). After complete dissolution the solution containing 21 wt.% Moo3, characterized by a molar ratio Mo/With - 1.5 and P/Mo - 0,08 has a pH of 2.2.

The composition and textural characteristics of the catalyst are shown in table 1. The ratio of Mo/Co catalyst is 1.5 and P/Mo and 0.08.

Under the conditions of test example 1, the catalyst provides a 90% yield of liquid oil and the sulfur content in them at level 90-100 ppm.

Example 7 (comparative 1, table 1)

Similar to example 1, except that the carrier is prepared by extrusion of a paste containing aluminum hydroxide (80 g) with peptizyde the addition of acetic acid (0.2 ml), followed by drying and heat treatment at 550°C for 4 hours

The calcined carrier contains γ-Al2About3and has the following characteristics: vaccum 0.9 cm3/g, specific surface 317 m2/g, pore volume of 0.71 cm3/g and average pore 90 Å.

The composition and textural characteristics of the catalyst lead is received in table 1. The ratio of Mo/Co according to the chemical analysis is 2.5 and P/Mo 0,15.

Under the conditions of test example 1, the catalyst provides a 99% yield of liquid oil and the sulfur content in them at the level 315-330 ppm.

Example 8 (comparative 2, table 1)

Similar to example 2, only the heat treatment of the catalyst is carried out in air atmosphere at 400°C for 4 hours

The composition and textural characteristics of the catalyst are shown in table 1. The ratio of Mo/Co according to the chemical analysis is 1.9 and P/Mo - 0,19.

Under the conditions of test example 1, the catalyst provides 85% yield of liquid oil and the sulfur content in them at the level 180-190 ppm.

Example 9 (comparative 3, table 1)

The composition and conditions of preparation of the carrier is similar to example 2.

The difference lies in the composition of the impregnating solution. For making it take 4.7 g of cobalt carbonate, of 5.48 g of citric acid monohydrate, 18,85 g of molybdenum oxide and 3 g of phosphoric acid (85%solution). After complete dissolution the solution containing 24 wt.% Moo3, characterized by a molar ratio Mo/ - 3.3 and P/Mo 0,2, has a pH of 0.65.

The composition and textural characteristics of the catalyst are shown in table 1. The ratio of Mo/Co catalyst is 3.4 and P/Mo 0,20.

Under the conditions of test example 1, the catalyst provides a 9% yield of liquid oil and the sulfur content in them at the level of 130-140 ppm.

Example 10 (comparative 4, table 1)

The composition and conditions of preparation of the carrier is similar to example 2.

The difference lies in the composition of the impregnating solution. For making it take 5.0 g of cobalt nitrate, 7.0 g of citric acid monohydrate, and 19.8 g of paramolybdate ammonium and 5.9 g of phosphoric acid (85%solution). After complete dissolution the solution containing 24 wt.% Moo3, characterized by a molar ratio Mo/Co - 3,0 and P/Mo - 0,4, has a pH of 0.75.

The composition and textural characteristics of the catalyst are shown in table 1. The ratio of Mo/Co according to the chemical analysis is 3.1 and R/Mo is 0.33.

Under the conditions of test example 1, the catalyst provides a 95% yield of liquid oil and the sulfur content in them at the level 200-220 ppm.

Example 11 (table 2)

Similar to example 1, except for preparing the media to 100 g of aluminum hydroxide obtained by the method of continuous deposition, containing 95% of pseudoboehmite and having a humidity of 75%, add 2.66 g of mordenite powder NaH-MOR with moisture content of 11% and 0.2 ml of 30%acetic acid, stirred Z-shaped mixer for 20 minutes the resulting mass is formed into extrudate through the die plate in the form of trilistnika diameter 2.3 mm Wet extrudate is cut into a length of 3-5 mm and air-dried. The extrudates calcined in air flow at 550°C for 4 h After proquali the project extrudates contain γ -Al2O3and NaH-MOR mass ratio of 91/9, have a capacity of 0.83 cm3/g, specific surface 248 m2/g, pore volume of 0.64 cm3/g and average pore 103 Å.

To prepare an impregnating solution using 6.0 g of cobalt carbonate, 7,10 g of monohydrate citric acid, 16 g of molybdenum oxide, 1.27 g of 85%phosphoric acid and 42 ml of water. After complete dissolution the solution contains of 23.4 wt.% Moo3, characterized by a molar ratio Mo/ - 2.2 and P/Mo 0,1, has a pH of 2.45.

To 30 g of the calcined extrudates type of 25.5 ml of impregnating solution, and incubated for 15 minutes. The impregnated extrudates are dried at room temperature, is subjected to heat treatment in a stream of air at 150°C for 8 hours

The catalyst contains, wt%: 20.7 Moo3, 5,1 Soo and 0.4 R, the ratio of Mo/Co according to the chemical analysis is 2.1 and P/Mo - 0,09. The catalyst has a specific surface area of 148 m2/g, pore volume is 0.33 cm3/g and average pore - 95 Å.

Of the extrudates of catalyst prepared fraction size 0.2-0.5 mm, 2 g fraction is loaded into the reactor and subjected to solifidian in the stream of hydrogen sulfide at 400°C for 2 h to Determine the yield of liquid oil and sulfur contents, which provides sulpicianus catalyst feeding him straight-run diesel fuel with the holding of sulfur, equal to 1.06 wt.%, and the following process conditions: a temperature of 340°C, a 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 for hydrotreatment of diesel fuel catalyst enables the reduction of sulfur in liquid petroleum products to the level of 420 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 70-80 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 460 ppm.

Example 12 (table 2)

Analogous to example 11, only for preparation of media, the paste is prepared from 100 g of aluminum hydroxide, 2.66 g of powder nikolamaster mordenite NiH-MOR and 0.2 ml of a 7%nitric acid. Michelsonii mordenite NiH-MOR receive the ion exchange 5 g of powder NaHMOR with 50 ml of ammonium acetate solution of Nickel, the concentration of Nickel acetate in solution - 0,125 M After carrying out the ion exchange of the zeolite powder was filtered, washed with aqueous ammonia solution and calcined at 400°C for 2 hours In the ion exchange receive NiH-OR, containing 2.52 wt.% Ni and having a ratio Si/Al - 5,3, specific surface 390 m2/g, pore volume to 0.18 cm3/g, the proportion of particles less than 8 μm is 90%.

Heat treatment conditions of the medium are similar to those of example 11. After calcination of the extrudates contain γ-Al2About3and NiH-MOR mass ratio of 91/9, have a vaccum 0,80 cm3/g, specific surface 239 m2/g, pore volume of 0.74 cm3/g and average pore 120 Å.

The composition of the impregnating solution and conditions for the heat treatment of the catalyst are the same as those of example 11. The composition and textural characteristics of the catalyst are shown in table 1. The ratio of Mo/(Co+Ni) in the catalyst according to the chemical analysis is 2.0 and P/Mo and 0.08.

When the test conditions of example 11, the catalyst provides 96-98% yield of liquid oil and the sulfur content in them at the level of 300 ppm at 340°C.

Example 13 (table 2)

Analogous to example 11, only for preparation of media, the paste is prepared from 100 g of aluminum hydroxide, 2,11 g of a powder of cobalt-substituted mordenite Son-MOR and 0.2 ml of a 7%nitric acid. Cobaltsomeone mordenite Son-MOR receive the ion exchange 5 g of powder NaMOR with 50 ml of ammonia solution of cobalt nitrate, the concentration of cobalt nitrate in a solution of 0.05 M After carrying out the ion exchange of the zeolite powder was filtered, washed in the NYM ammonia solution and calcined at 400° C for 2 hours. In the ion exchange gain of Son-MOR containing 0.4 wt.% With and having a ratio Si/Al - 5,7, specific surface 395 m2/g, micropore volume - 0,18 cm3/year

Heat treatment conditions of the medium are similar to those of example 11. After calcination of the extrudates contain γ-Al2O3and Son-MOR mass ratio of 93/7 have vaccum 0,90 cm3/g, a specific surface area of 270 m2/g, pore volume of 0.54 cm3/g and average pore 85 Å.

To prepare an impregnating solution using 5.0 g of cobalt carbonate, 1.0 g of Nickel carbonate, 7,10 g of monohydrate citric acid, 16 g of molybdenum oxide, 1.27 g of 85%phosphoric acid and 42 ml of water. After complete dissolution the solution contains of 23.4 wt.% Moo3, characterized by a molar ratio Mo/(Co+Ni) - 2.2 and P/Mo 0,1, has a pH of 2.45.

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, is subjected to heat treatment in a stream of air at 150°C for 10 hours Composition and textural characteristics of the catalyst are shown in table 1. The ratio of Mo/(Co+Ni) in the catalyst according to the chemical analysis is 2.3, P/Mo - 0,12.

When the test conditions of example 11, the catalyst provides 96-98% yield of liquid products and the content of the sulfur in them at the level of 350 ppm at 340° C.

Example 14 (comparative prototype, table 2)

As the carrier used extrudates, obtained by extrusion of a paste based on pepsirefresh of aluminum hydroxide continuous deposition, with subsequent stages of drying and calcination in air stream at 550°C for 4 h Dimensions of extrudates: diameter of 1.3-1.4 mm, length 4-5,2 mm extrudates are characterized by a specific surface area of 275 m2/g, pore volume of 0.82 cm3/g and an average pore 119 Ådetermined from the adsorption isotherms of nitrogen.

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.

To 30 g of the calcined extrudates add 27 ml of impregnating solution, and incubated for 15 minutes. The 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 composition and textural characteristics of the catalyst are shown in Table 1. The ratio of Mo/Co according to the chemical analysis is 2.4 and P/Mo - 0,26.

When y is s test of example 11, 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.

It is seen that the inventive compositions of Co(Ni)-Mo catalysts containing compounds of molybdenum, cobalt and/or Nickel) and phosphorus in a molar ratio Mo/(Co+Ni) - 1.5 to 2.5 and P/Mo 0,08-0,15, disperision on a porous alumina carrier with modifying additive of zeolite, in particular ZSM-5, BEA, MOR, and Y (examples 1-6 and 11-13), have a high gidroobesserivaniya activity. At a temperature of 350°C, pressure of 3.5 MPa and a ratio of hydrogen/fuel - 500 claimed Co(Ni)-Mo catalysts depending on the structural type zeolite, included in the alumina carrier in the amount of 5-15 wt.%, provide diesel hydrodesulphurization unit fractions to the level of 30-165 ppm, while the conversion of sulfur compounds is 98,4-99,7, and the yield of liquid oil products 92-98%. Under these conditions, on Co-Mo catalyst similar chemical composition in the case of using alumina media without modifying additive zeolite (example 7) is the hydrodesulphurization unit to the level 315-330 ppm. Among these structural types of zeolites ZSM-5, BEA, MOR, and Y is preferable to the use of mordenite, ZSM-5 and BEA, as in H-form and cation-exchanged form.

When the molar ratio Mo/(Co+Ni) in the catalyst is in the range of 1.5-2.5 and R/Mo in the range of 0.08 to 0.15, the content of the active component mainly in the number 16-21 wt.% Moo3and 4-6 wt.% COO and/or NiO, is DOS is enough to ensure high gidroobesserivaniya activity of Co(Ni)-Mo catalysts, prepared on modified zeolites alumina media. In the present limits of the content of Moo3and CoO(NiO) and the ratio of Mo/(Co+Ni) and P/Mo, Co(Ni)-Mo catalysts at a temperature of 350°C, pressure of 3.5 MPa and a ratio of hydrogen/fuel - 500 provide a Hydrotreating of diesel fuel from the sulfur compounds to sulfur content not exceeding 165 ppm. Thus, the samples No. 2, 5 and 6, containing compounds of molybdenum and cobalt and/or Nickel dispersed on the carrier with the addition of ZSM-5, provide a hydrodesulphurization unit of diesel fuel up to a level of not higher than 130 ppm of sulfur.

It is seen that at the close oxide content molibden, for example, 18-19 wt.% the increase in molar ratio Mo/(Co+Ni) in the catalyst is higher than 2.5, for example to 3.4 (example 9), leads to a decrease gidroobesserivaniya the activity of the catalyst. The tendency to decrease gidroobesserivaniya the catalyst activity observed for catalysts, which is characterized by a molar ratio Mo/(Co+Ni) below 1.5, but in this case, the decrease of activity is not as strong. So, Co-Mo catalysts with content 16-19 wt.% Moo3and the ratio of Mo/Co equal to 1.5 (example 6), 2.1 (example 2) and 3.4 (example 9), provide the hydrodesulphurization unit diesel fuel sulfur level 90-100, 65-80 and 130-140 ppm, respectively, at a temperature of 350°C, pressure of 3.5 MPa and a ratio of hydrogen/fuel - 500.

the alignment activity of samples 2 and 8 shows that heat treatment of air-dried samples of Co(Ni)-Mo catalysts is preferably carried out in an atmosphere of nitrogen or air at temperatures of 200°C and below. With increasing heat treatment temperature to 400°With a tendency to decrease gidroobesserivaniya activity. Samples No. 2 and 8, subjected to heat treatment in a stream of air at 200 and 400°To provide for the reduction of sulfur content in diesel fuel to 1.06 wt.% up to 65-80 and 180-190 ppm, respectively.

Comparison of the activity of samples 9 and 10, having a similar chemical composition, shows that the use as precursors of active compounds of molybdenum oxide and cobalt carbonate (example 9) is preferred, however, does not exclude the possibility of using paramolybdate ammonium and nitrate cobalt(Nickel) (example 10) for the preparation of Co(Ni)-Mo catalyst containing compounds of molybdenum and cobalt and/or Nickel dispersed on a modified zeolite alumina carrier. At a temperature of 350°and a ratio of hydrogen/fuel 500, samples 9 and 10 provide a sulfur content in diesel fuel at the level of 130-140 and 200-220 ppm, respectively.

Activity comparison of samples No. 11 to 13 and 14, having a similar composition of the active component, shows that the introduction of the additive zeolite, in particular mordenite, alumina floor has the positive impact on gidroobesserivaniya activity of Co(Ni)-Mo catalyst. Samples 12 and 13 are prepared on alumina carriers with the addition of mordenite in cation-exchanged form, provide a Hydrotreating of diesel fuel to the level of 300-350 ppm at a temperature of 340°and the frequency of circulation of the hydrogen-containing gas is 300, which is lower in comparison with sample No. 14, prepared on the alumina carrier. The introduction of the alumina carrier of the additive zeolite of the following structural types: ZSM-5, MOR, BEA, Y, gives the media a developed specific surface area (not less than 230 m2/g)porous structure (not less than 0.6 cm3/g) with a narrow distribution of the pore size (mainly with pores 80-140 Å), high Pentecostal acidity.

The presence of zeolite in the catalyst composition has a positive effect on the stability of the catalyst to deactivation by hydrogen sulfide formed by the reaction of the hydrogenolysis of C-S communication sulfur aromatic compounds, due to the ability of zeolites to reversibly adsorb the hydrogen sulfide. So, after exposure to a temperature of 370°C for 7-9 h samples prepared on alumina carriers with modifying additive of zeolite and without it, provide the hydrodesulphurization unit diesel fuels to the level of 370-420 and 440-450 ppm, respectively.

The inventive catalyst composition provides improved gidroobesserivaniya activity of Co(Ni)-Mo was pushing the congestion at moderate temperatures (320-340° C) and pressure (up to 3.5 MPa) process hydrodesulphurization unit diesel fuels while increasing the stability of the catalysts for the decontamination of hydrogen sulfide formed by hydrogenolysis reactions of sulfur organic compounds. The inventive catalyst composition provides deep Hydrotreating of diesel fuel in conditions close to the conditions at operating units for hydrotreatment of diesel fuel, i.e. at temperatures 340-350°C, pressure of 3.5 MPa, and the ratio of the circulation of the hydrogen-containing gas 300-500 m2/m3of raw materials.

1. The catalyst for processes of diesel hydrodesulphurization unit fractions, including active component metal oxides VIII and VIB groups deposited on the alumina carrier, characterized in that as the carrier composition contains alumina and zeolites: ZSM-5, mordenite, WEAH or Y, with the following content, wt.%: zeolite 5-15, alumina-85-95; as an active component is molybdenum oxide, cobalt oxide and/or Nickel and phosphorus, the catalyst has a specific surface area of 100-190 m2/g, pore volume of 0.3-0.5 cm3/g, predominant pore 80-120Å and is characterized by bands 12400-14000 cm-1and 14200-18500 cm-1in the electronic spectra of diffuse reflection.

2. The catalyst according to claim 1, otlichayushiesya, the media contains H-form ZSM-5, mordenite, WEAH or Y at the following mass ratio, wt.%: zeolite 5-15, alumina - rest.

3. The catalyst according to claim 1, characterized in that the medium contains a Ni - or Co-substituted ZSM-5, mordenite, WEAH or Y when the next mass cations of Nickel or cobalt in the zeolite, wt.%: Ni or Co - 0,5-3, zeolite - rest.

4. The catalyst according to claim 1, characterized in that as the active component contains, wt%: molybdenum oxide of Moo3the number of 16.0-29,0, cobalt oxide COO and/or Nickel oxide NiO in the number of 3-8, and phosphorus of 0.1-0.5, medium of rest, when the atomic ratio of Mo/(Co+Ni) - 1.5 to 2.5 and P/Mo - 0,08-0,15.

5. The catalyst according to claim 1, characterized in that it has the shape of a cylinder or trilistniku.

6. A method of obtaining a carrier for catalysts processes of diesel hydrodesulphurization unit fractions, characterized in that it includes the precipitation of aluminum hydroxide, the introduction of aluminum hydroxide additive of zeolite ZSM-5, mordenite, WEAH or Y in the H form or cation-substituted form in the amount of 5-15 wt.% in the calculation of the finished product, and peptizyme supplements monobasic acid, forming by extrusion, drying and calcination at 450-600°; and provides media specific surface 230-400 mesh m2/g, pore volume of 0.5-0.9 cm3/g, predominant pore 80-120 Å.

7. The method according to the .6, characterized in that as peptizyme supplements monobasic acid, nitric or acetic acid, which is injected in an amount to provide a molar ratio of acid/Al2About3in the range 0.001-0.07 respectively.

8. A method of producing a catalyst for processes of diesel hydrodesulphurization unit fractions, comprising a carrier impregnated comprehensive solution of the active component with a subsequent heat treatment in a stream of air or nitrogen at a temperature of not higher than 200°C, characterized in that the medium contains a composition of aluminum oxide and N-form or cation-substituted form of zeolite ZSM-5, mordenite, WEAH or Y, with the following content, wt.%: zeolite 5-15, alumina - 85-95; impregnating solution of the active component contains molybdenum oxide and carbonate of cobalt and/or Nickel, stabilized with phosphoric acid and citric acid to the atomic ratio P/Mo in the range of 0.08 to 0.15, and pH in the range of 1.3 to 3.5.

9. 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 5 or a catalyst prepared according to item 8.

10. The method according to claim 9, wherein 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 is STI 2 h -1, the volumetric ratio of hydrogen/fuel 300-500.



 

Same patents:

The invention relates to methods of producing diesel fuels and can be used in the refining industry

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.

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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.

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EFFECT: the invention ensures simplification of the production process.

3 cl

FIELD: chemical industry; methods of preparation of the platinum hydrophobic catalyst used for separation of the isotopes of hydrogen and water.

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EFFECT: the invention ensures, that the prepared catalyst possesses the high catalytic activity (the exchange constant кe ˜ 10÷20 s-1), stability (no less than three years), radiation resistance (up to the dose of the irradiation - 100 Mrad).

4 cl, 10 ex, 6 tbl, 2 dwg

FIELD: petroleum processing and petrochemical process catalysts.

SUBSTANCE: hydrofining catalyst is composed of, wt %: NiO 2.5-4.0, MoO3 8.0-12.0, Na2O 0.01-0.08, La2O3 1.5-4.0, P2O5 2.0-5.0, B2O3 0.5-3.0, and Al2O3 the rest. Preparation of the catalyst involves impregnation of sodium oxide-containing carrier with active components: nickel nitrate and ammonium paramolybdate solution followed by drying and calcination. In particular, sodium oxide-containing aluminum hydroxide is mixed with boric acid solution and nitric acid solution of lanthanum carbonate, resulting carrier is dried and calcined, after which impregnated with nickel nitrate and ammonium paramolybdate solution at pH 1.5-3.0 and temperature 40-80°C in presence of phosphoric acid.

EFFECT: enhanced efficiency of hydrofining raw materials comprising elevated amounts of unsaturated hydrocarbons.

2 cl, 2 ex

FIELD: chemical industry; oil-refining industry; other industries; methods of production of the catalytic microporous fine-dispersed materials.

SUBSTANCE: the invention is pertaining to the method of production of the catalytic microporous fine-dispersed material, which is used in such processes, as purification of the oil fractions, purification of the sewage disposal, the catalytic conversion of the exhaust gases exiting from the combustion engines. The method allows to produce the catalytic microporous fine-dispersed material with the coating of the rare-earth metal oxide, in which the quantity of the metal oxide deposited on it is high without the risk for efficiency of the material. At that the rare-metal oxide is deposited on the outer surfaces of the indicated material and may be within the interval of 20-70 mass % with respect to with respect to the total equivalent content of the rare-earth metal oxide and the microporous fine-dispersed material. The method provides for the combination of the quantity of the colloid dispersion of the hydrate of the rare-earth metal oxide with the compatible microporous fine-dispersed material with formation of the suspension and the thermal treatment of the indicated suspension for the rare-earth metal oxide fixation on the outer surfaces of the indicated material. At that the indicated microporous fine-dispersed material has the average size of the pores less than 20 Å, and the indicated colloid dispersion has the particle size of the particles of not less than 20 Å. The invention also presents the catalytic free-loose fine-dispersed material with the rare-earth metal oxide coating containing the ceolite fine-dispersed material, the rare-earth metal oxide. At that the indicated ceolite fine-dispersed material has the average size of the pores less than the size of the particles of the indicated rare-earth metal oxide, and more than 20 mass % of the indicated rare-earth metal oxide is on the outer surfaces the indicated ceolite fine-dispersed material with respect to the total equivalent content of the rare-earth metal oxide and the ceolite. The ceolite free-loose fine-dispersed material having the high contents of the rare-earth metal oxide has the tendency to be the very stable material.

EFFECT: the invention ensures production of the catalytic microporous fine-dispersed material with the coating of the rare-earth metal oxide without the risk for efficiency of the material and the ceolite free-loose fine-dispersed material having the high contents of the rare-earth metal oxide has the tendency to be the very stable material.

31 cl, 11 ex, 3 tbl

FIELD: shift reaction catalysts.

SUBSTANCE: invention relates to iron oxide-containing catalysts generally used for high-temperature shift reactions wherein gas stream containing water steam and carbon monoxide is passed over catalyst at temperature within a range of 350 to 550°C to convert carbon monoxide into carbon dioxide with simultaneous formation of hydrogen. Catalyst is prepared via precipitation of composition containing ferrous and ferric iron and chromium(III) with a base, ferrous iron being partly oxidized by an oxidant into ferric iron. Further formation of resulting precipitate into formed catalyst blocks is effected at temperature above 200°C. Invention also provides a high-temperature shift reaction process using above catalyst blocks.

EFFECT: avoided need of catalyst restoration stage resulting in improved catalyst strength and activity.

10 cl, 2 tbl, 2 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: catalyst containing platinum, rhenium, antimony, and chlorine on alumina are prepared by impregnation of carrier with aqueous solution of compounds of indicated elements, antimony being deposited as first or second component. Once antimony or platinum-antimony combination, or rhenium-antimony combination deposited, catalyst is dried at 130°C and then calcined in air flow at 500°C. Reduction of catalyst is performed at 300-600°C and pressure 0.1-4.0 MPa for 4 to 49 h. After deposition of antimony or two elements (platinum-antimony or rhenium-antimony) and drying-calcination procedures, second and third or only third element are deposited followed by drying and calcination. Final reduction of catalyst is accomplished in pilot plant reactor within circulating hydrogen medium at pressure 0.3-4.0 MPa and temperature up to 600°C for a period of time 12 to 48 h.

EFFECT: enhanced aromatization and isomerization activities of catalyst and also its stability.

2 cl, 1 tbl, 8 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: 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: carbon materials.

SUBSTANCE: invention relates to porous carbon materials and, more specifically, to carbon catalyst supports and sorbents. Preparation of catalyst support is accomplished by mixing carbon material with gaseous hydrocarbons at 750-1200°C until mass of carbon material increases by 2-2.5 times, after which resulting compacted material is oxidized, said initial carbon material being preliminarily demetallized carbon nanofibers.

EFFECT: increased sorption capacity of material.

1 tbl, 6 ex

FIELD: carbon materials.

SUBSTANCE: invention relates to porous carbon materials and, more specifically, to carbon catalyst supports and sorbents. Preparation of catalyst support is accomplished by treating carbon black with hydrocarbon gas at heating and stirring until mass of carbon material increases by 2-2.5 times, after which resulting compacted material is oxidized, said hydrocarbon gas being gas originated from liquid hydrocarbon electrocracking and said treatment being carried out at 400-650°C.

EFFECT: simplified technology.

1 tbl, 6 ex

FIELD: polymerization processes and catalysts.

SUBSTANCE: invention relates to preparing supported titanium-magnesium catalyst for production of polyethylene and superhigh-molecular weight polyethylene via suspension polymerization of ethylene in hydrocarbon solvent. Invention provides a method for preparing supported ethylene polymerization catalyst containing titanium compound on magnesium-containing support, which is prepared by interaction of dissolved organomagnesium compound having following composition: MgPh2·nMgCl2·mR2O, wherein R represents butyl or isoamyl, n=0.37-0.7, and m=1-2, with compounds inducing conversion of organomagnesium compound into solid magnesium-containing support. As such compounds, there is used a composition including product of reaction of alkylsilane R'kSi4-k, wherein R is alkyl or phenyl and k=1, 2, with silicon tetraalkoxide Si(OEt)4 at molar ratio 2-4, respectively, and a dialkylaromatic ether. Catalyst is characterized by high activity at temperatures ≤60°C and particle size within a range 5.5 to 3.0 μm. Catalyst allows a polymer powder with average particle size ≤150 μm, narrow particle size distribution, and high loose density (≥250 g/L) to be obtained.

EFFECT: enhanced low-temperature catalyst activity and selectivity.

3 cl, 1 tbl, 15 ex

FIELD: production of pigments and catalysts based on titanium dioxide, in particular, process for treatment of titanium dioxide for removal of sulfur, in particular sulfates.

SUBSTANCE: method involves treating calcined titanium dioxide at elevated temperatures using aqueous solution containing one or more ammonium compounds; separating titanium dioxide from aqueous solution and drying titanium dioxide. Ammonium compounds preferably used in treatment process are ammonium acetate or ammonium chloride.

EFFECT: increased efficiency in cleaning of titanium dioxide from sulfur, in particular sulfates.

9 cl, 5 tbl, 5 ex

FIELD: catalyst carriers.

SUBSTANCE: invention relates to structure and composition of carrier based on grid-structured tissue of glass, silica, or another interaction fiber treated with formulations imparting rigidity to grids and preventing deformation-caused destruction of fibers, which carrier is used mainly to retain photocatalytically active material on its surface, but also suitable to retain catalysts exhibiting activity in the absence of light. Provided is catalyst carrier constituted by one or several arranged in parallel layers of corrugated grid made from inorganic woven fibers and impregnated with binding material or constituted by one or several arranged in parallel layers of non-corrugated grid also made from inorganic woven fibers and impregnated with binding material.

EFFECT: increased catalyst retention ability and increased area of illuminated photocatalyst surface.

3 cl, 3 dwg, 8 ex

FIELD: alternate fuels.

SUBSTANCE: invention relates to production of synthetic gas via catalytic hydrocarbon conversion in presence of oxygen-containing gases and/or water steam as well as to catalysts suitable for this process. Invention provides catalyst, which is complex composite constituted by supported precious element, or supported mixed oxide, simple oxide, transition element, wherein support is a metallic carrier made from metallic chromium and/or chromium/aluminum alloy coated with chromium and aluminum oxides or coated with oxides of chromium, aluminum, or mixtures thereof. Catalyst preparation procedure and synthetic gas production process are also described.

EFFECT: increased conversion of hydrocarbons, selectivity regarding synthetic gas, and heat resistance of catalyst at lack of carbonization thereof.

4 cl, 3 tbl, 9 ex

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