Catalyst, method for preparation thereof, method for preparing carrier for this catalyst, and diesel fraction desulfurization process

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

 

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 sulfur-containing 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.

In the patent RU 2074025 described a method of producing catalyst for Hydrotreating petroleum fractions containing, wt.%: 14-21 molybdenum oxide, 3-8 Nickel oxide or cobalt oxide, 0.5 to 6 phosphoric anhydride, alumina rest, by applying the active compounds of components to aluminum oxide by coprecipitation of salts of metals of the VIII and VI groups of the Periodic system and phosphorus, followed by forming a catalytic mass in the form of extrudates, drying and calcining the obtained granules, characterized in that the application of active ingredients is carried out by introducing them to the aluminum hydroxide in the form of a complex metal salt solution VIII and VI groups, stabilized with phosphoric acid, provided that the pH of the solution of phosphoric acid is 0.5 to 2.5 at 40-60°C.

In the patent RU 2137541 describes a method for the catalysis of the ora for Hydrotreating of crude oil, including the precipitation of aluminium hydroxide sulphate method, the introduction of aluminum hydroxide salts of molybdenum and Nickel, forming, extrusion, drying, calcining, wherein prior to depositing the active components of the aluminum hydroxide is heated at a temperature of 50-80°With continuous stirring, then enter Paladino paramolybdate ammonium and nitrate Nickel with intermediate heating of molybdenum aluminum hydroxide with constant stirring for 30 min, and treated the resulting mass with humidity 68-70 wt.% monobasic mineral acid (nitric or hydrochloric) to a pH in the range 4-6.

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 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 PR is for drinking, preparing catalysts gidromassazhnye diesel fractions, it is recommended to use calcined media having a specific surface area of 200-300 m2/g, pore volume of 0.5-0.9 cm3/g and an apparent density of 0.5 to 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 the 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, you want 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 molybdenum and is of lframe, ammonium salts of molybdenum and tungsten acid (paramolybdate and paraformat ammonium), molybdenum or tungsten acid, in some cases phosphomolybdenum or phosphonoformate 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, it is most often 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 AFL is stvie educational opportunities 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 by zakoksovanie the catalyst surface hydrocarbon components of diesel fuel. The disadvantage of this IU the ode 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 outdoor activities is complex media (up to 6 atoms of Mo on nm 2Al2O3helps 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 CoAl2O4at the stage of impregnation and heat treatment, since the latter when the pretreatment of the catalyst in the sulfur-containing fluid (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), to the impregnating solution, by annealing the 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 Tr is traditionally achieved for Co(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.

The patent (US 5686374, B01J 29/10, 11.11.97) describes the catalyst wadrobes is eridania hydrocarbons, 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 V, and/or zinc oxide, and, if necessary, the boron compound. 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 fuels. The catalyst have which allows 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 of 93.3-93,5% when the sulfur content to 0.72 wt.%, a pressure of 3 MPa, 380°C, space velocity of the raw materials 2.5 h-1and the frequency of circulation of the hydrogen-containing gas of 400 nm3/m3 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 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.

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, a solution containing molybdenum oxide, cobalt carbonate and phosphoric acid, in an amount necessary for the introduction of the catalyst is not less, wt.%: 17-25 NGO 3, 1-6 COO or NiO 1-4 and P, provided that the molar ratio P/Moo3in the solution above 0,1, mainly of 0.2, and a 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 the nitrates of cobalt or Nickel. In the case of molybdenum oxide as the precursor of the metal of group VIII is better to use the carbonates 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 paramolybdate AMM is occurring 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 2006/0054536, 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 NGO3(mainly 26-29), 1-15 COO and/or NiO (5,6-5,8), 1,5-8 P2O3(mainly 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 its high content of phospho who and, 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 is to provide a composition and method of making highly efficient 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 optimizing the texture of the catalyst containing compounds of molybdenum and cobalt and/or Nickel dispersed on the surface of the modified alumina carrier, and optimizing the composition of the active complex.

Optimization of the texture of the medium is achieved by the fact that as the carrier of the calcined catalyst contains alumina, modified at the stage of preparation of extrudates CA - or Na-form of montmorillonite. Introduction Zola montmorillonite in the molding composition on the basis of aluminum hydroxide obtained od of them from deposition methods (continuous or periodic) or by hydrolysis of aluminum isopropylate, ensures high specific surface of the carrier (not below 200 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 optimum acidity and high mechanical strength.

Introduction montmorillonite 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, both due to the increasing acidity of the medium, and due to the presence of montmorillonite cations CA and Mg. In addition, the introduction of media montmorillonite 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.

Optimization of the composition of the active complex and its uniform application is achieved by the fact that the content of compounds of molybdenum is in the range 14-29 wt.% Moo3mainly 16-21 wt.%, and the ratio of Mo/Co and/or Mo/Ni varies in the range of 1.3 to 2.6, which is sufficient to ensure high activity in diesel hydrodesulphurization unit fractions. When the specified content of Moo3and the ratio of Mo/Co and/or Mo/Ni is formed on the optimum content of the so-called "CoMoS II centers, namely doped with cations of cobalt or Nickel plots of the layered structure MoS2. To increase the uniformity of application of the active complex uses impregnating solutions containing molybdenum oxide and cobalt carbonate, 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 within 0,08-0,1 is sufficient to ensure the stability of 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, which leads to the formation of cristallizing phases Co3O4and CoAl2O4during annealing. 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 up to 240°excludes active destruction complex. These techniques, used for the preparation of the catalyst, provide formation of a large number of "Como II centers and increase the activity of the catalyst at moderate temperatures of diesel hydrodesulphurization unit fractions.

In addition, the reduction of the giving 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, which prevents the adsorption of these centers hydrocarbons and deactivation due to coking.

The media, and hence the catalyst, mainly 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 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. 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 With the o and Ni-Mo catalysts, respectively, and the ratio of the circulation of the hydrogen-containing 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 were tested in the form of fractions of size 0.25-0.5 mm, which was prepared by crushing and dispersion of the source of the extrudates. A portion of the catalyst mass of 2.0 g were placed in a vertical flow reactor made of stainless steel having an inner diameter of 8 mm, while the height of the catalyst layer was 50±10 mm Above the catalyst layer for uniform mixing and heating of the feedstock was placed a layer of silicon carbide (particle 1-2 mm), which was 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 was also separated from the catalyst layer pad of fiberglass.

The catalysts were sliderule at atmospheric pressure in a stream of hydrogen sulfide, which began to serve it at room temperature at a rate of 1 l/h, the Reactor was heated from room temperature to 400°C for 30 min and then continued sulfatirovnie for 2 hours and Then the reactor by means of shut-off valves were cut simultaneously from the supply lines and discharge of hydrogen sulfide and cooled to room temperature is.

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 of 1.06% S (10600 ppm)

Flash point (closed Cup) 66,9°

Fractional composition of 50% of the volume distills at 292°

96% of the volume distills at 366°C.

The reactor solifidianism catalyst was placed in a thermostat electric heating, filled with hydrogen to a pressure of 3.5 MPa at room temperature, after which began 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 started warming up of the reactor from room temperature to 340°that was conducted within 35-40 minutes and the process was carried out at a temperature of 340°and a pressure of 3.5 MPa.

At the exit of the reactor products have passed through the capillary, stainless steel, internal diameter 2 mm, which was cooled to 60-70°C, after which he enrolled at the site of discharge pressure to atmospheric. Next, the products were cooled in the refrigerator separator, provided with a water jacket and was divided into gas and liquid are their. 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 was thrown out without any analysis, then every 2 h was determined by mass output of diesel fuel and the sulfur content in it.

About the activity of the catalyst to be judged by the content in the residual oil sulfur. Mass content of sulfur in liquid petroleum products was determined without prior removal of dissolved therein sulfide. To determine the sulfur content used 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 : 1) showed 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 diesel fractions catalysts were subjected to exposure to elevated temperatures 370°With 6-9 h (to speed up the processes of decontamination), and then measured the activity of the catalysts at a temperature of 340°C, pressure of 3.5 MPa, and the ratio of the circulation of the hydrogen/feedstock 300.

In some experiments, the definition and the activity of the catalysts was carried out at a temperature of 350° C, a pressure of 3.5 MPa, the flow rate of the liquid fuel 2 h-1and the ratio of hydrogen/feedstock 500, conditions modificirovanie similar to those described above.

The invention is illustrated by the following examples.

Example 1 (see table 1).

To 80 g of aluminum hydroxide obtained by the method of periodic deposition and containing 95% of pseudoboehmite, humidity 76% type of 8.27 g of CA-montmorillonite dispersed in water and having a humidity 59%, and 0.2 ml of a 7%nitric acid, stirred for 20 min on Z-shaped mixer. The resulting mass is formed into extrudates. The extrudates calcined in air flow at 550°C for 4 hours After calcination of the extrudates contain γ-Al2About3and CA-montmorillonite in a weight ratio of 85/15, have a specific surface area of 276 m2/g, pore volume of 0.85 cm3/g and average pore 106 Å.

For preparation of the impregnating solution to 6.0 g of cobalt carbonate add 42 ml of distilled water and heated to a temperature of 80°C. Then with stirring portions 7,14 g of citric acid monohydrate, while there has been intense emission of CO2. Waiting for the complete dissolution of the precipitate, add to 14.7 g of molybdenum oxide Moo3and 1.18 g of phosphoric acid (85%solution). Continue to stir the solution at a temperature of 80°until dissolved. After olego dissolution solution volume of 50 ml The solution contains a 22.4 wt.% Moo3, characterized by a molar ratio Mo/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 Impregnated extrudates are dried in a stream of nitrogen and then in the muffle in an atmosphere of air at 150°C for 10 hours

The content of molybdenum oxide in the catalyst is 19.0 wt.% (here and further in the calculation of Moo3), cobalt oxide of 4.9 wt.% (here and below, based on COO) and phosphorus 0.4 wt.% (R).

The catalyst after calcination at 150°has a specific surface area (Sbeats) 156 m2/g, pore volume (VΣ) 0,33 cm3/g and the average radius of the pores (Dcp) - 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 hours

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: 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 for hydrotreatment of diesel fuel rolled the ATOR enables the reduction of sulfur in liquid petroleum products to the level of 150-180 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 230 to 250 ppm.

Example 2 (see table 1).

Similar to example 1, except for preparing an impregnating solution using 9,04 g of cobalt carbonate, 10,63 g of citric acid monohydrate, and 15.3 g of molybdenum oxide and of 1.23 g of 85%phosphoric acid. The resulting solution contains a 22.4 wt.% Moo3has a molar ratio of Mo/Co, is equal to 1.4, and P/Mo of 0.1 and a pH of 1.9.

After impregnation 30 g of the carrier from example 1, containing aluminum oxide and CA-montmorillonite in a weight ratio of 85/15, with 25.5 ml of solution, the catalyst is dried and calcined under the conditions of example 1. The textural characteristics of the catalyst and the composition of the active component are given in table 1.

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 210-230 ppm at 340°C.

Example 3 (see table 1).

Similar to example 1, except for preparing an impregnating solution used to 5.03 g of cobalt carbonate, of 5.92 g of monohydrate citric acid is you, of 14.7 g of molybdenum oxide and of 1.17 g of 85%phosphoric acid. The resulting solution contains a 22.4 wt.% Moo3has a molar ratio of Mo/Co, 2.4, and P/Mo of 0.1 and a pH of 1.7.

After impregnation 30 g of the carrier from example 1, containing aluminum oxide and CA-montmorillonite in a weight ratio of 85/15, with 25.5 ml of solution, the catalyst is dried and calcined under the conditions of example 1. Textural characteristics and the composition of the catalyst is summarized in table 1.

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 220 to 250 ppm at 340°C.

Example 4 (see table 1).

Similar to example 1, except for preparing an impregnating solution using the 4.65 g of cobalt carbonate, vs. 5.47 g of citric acid monohydrate, 14,66 g of molybdenum oxide and 1.18 g of 85%phosphoric acid. The solution contains a 22.4 wt.% Moo3has a molar ratio Mo/With 2.6 and P/Mo 0.1 and a pH of 1.7.

After impregnation 30 g of the carrier from example 1, containing aluminum oxide and CA-montmorillonite in a weight ratio of 85/15, with 25.5 ml of solution, the catalyst is dried and calcined under the conditions of example 1. Textural characteristics and the composition of the catalyst is summarized in table 1.

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 370 ppm at 340°C.

PR is measures 5 (see table 1).

Similar to example 1, except for preparing an impregnating solution use of 6.17 g of cobalt carbonate, 7,26 g of citric acid monohydrate, 17,94 g of molybdenum oxide and 1.43 g of 85%phosphoric acid. The solution contains of 25.4 wt.% Moo3has a molar ratio of Mo/Co 2.4 and P/Mo of 0.1 and a pH of 1.8.

After impregnation 30 g of the carrier from example 1, containing aluminum oxide and CA-montmorillonite in a weight ratio of 85/15, with 25.5 ml of solution, the catalyst is dried and calcined under the conditions of example 1. Textural characteristics and the composition of the catalyst is summarized in table 1.

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 250-280 ppm at 340°C.

Example 6 in table 1)

To 80 g of aluminum hydroxide obtained by the method of periodic deposition and containing 95% of pseudoboehmite, with a humidity of 75 % add to 3.67 g of CA-montmorillonite dispersed in water and having a humidity 59%, and 0.2 ml of a 7%nitric acid, mixed and formed into extrudates. The extrudates calcined in air flow at 550°C for 4 hours After calcination of the extrudates contain γ-Al2About3and CA-montmorillonite in a mass ratio of 93/7, have a specific surface area of 238 m2/g, pore volume of 0.85 cm3/g and average pore 109 Å.

The solution was prepared analogously to example 1, is only to prepare the solution take 7,12 g of cobalt carbonate, of 8.37 g of citric acid monohydrate, 18,11 g of molybdenum oxide and 1.45 g of 85%phosphoric acid. The resulting solution contains of 25.4 wt.% Moo3has a molar ratio of Mo/Co, equal to 2.1, and P/Mo of 0.1 and a pH of 1.5.

To 30 g of carrier type of 25.5 ml, incubated 15 min and then the impregnated carrier is dried at room temperature and subjected to heat treatment at 150°C for 8 h in a stream of nitrogen.

Textural characteristics and the composition of the catalyst is summarized in table 1.

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 280-300 ppm at 340°C.

Example 7 (see table 1).

To 80 g of aluminum hydroxide obtained by the method of periodic deposition and containing 95% of pseudoboehmite, with a humidity of 75% type of 2.56 g of CA-montmorillonite dispersed in water and having a humidity 59%, and 0.2 ml of a 7%nitric acid, mixed and formed into extrudates. The extrudates calcined in air flow at 550°C for 4 hours After calcination of the extrudates contain γ-Al2About3and CA-montmorillonite in a mass ratio of 95/5, have a specific surface area of 245 m2/g, pore volume of 0.85 cm3/g and average pore 115 Å.

An impregnating solution is prepared analogously to example 6.

To 30 g of carrier type of 25.5 ml, incubated 15 min and onwards the impregnated carrier is dried and subjected to heat treatment at 150° C for 8 h in a stream of nitrogen. Textural characteristics and the composition of the catalyst is summarized in table 1.

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 280-300 ppm at 340°C.

Example 8 (see table 1).

To 80 g of aluminum hydroxide obtained by the method of periodic deposition and containing 95% of pseudoboehmite, with a humidity of 70% of type 9,52 g of Na-montmorillonite dispersed in water and having a humidity 72%, stirred for 20 min and formed into extrudates. The extrudates calcined in air flow at 550°C for 4 hours After calcination of the extrudates contain γ-Al2O3and Na-montmorillonite in a mass ratio of 90/10, have a specific surface area of 229 m2/g, pore volume of 0.7 cm3/g and average pore 75 Å.

An impregnating solution is prepared analogously to example 6.

To 30 g of carrier add 21 ml, incubated 15 min and then the impregnated carrier is dried and subjected to heat treatment at 150°C for 8 h in a stream of nitrogen.

Textural characteristics and the composition of the catalyst is summarized in table 1.

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 240-270 ppm at 340°C.

Example 9 (see table 1).

The method of preparation of the medium and its composition EN is a logical example 1.

For preparation of the impregnating solution used 5,09 g of cobalt carbonate, 2,19 g Nickel carbonate, of 8.37 g of citric acid monohydrate, 18.11 molybdenum oxide and 1.45 g of 85%phosphoric acid. The solution contains of 25.4 wt.% Moo3has a molar ratio (Mo/Co+Mo/Ni), equal to 2.1, and P/Mo 0.1 and a pH of 1.5.

To 30 g of the carrier from example 1 (with a ratio of Al2O3to CA-montmorillonite equal to 85/15, and pore volume of 0.85 cm3/g) type of 25.5 ml, incubated 15 min and then the impregnated carrier is dried and subjected to heat treatment at 150°C for 8 h in a stream of nitrogen.

Textural characteristics and the composition of the catalyst is summarized in table 1.

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 250-290 ppm at 340°C.

Example 10 (table 2)

The preparation method of the carrier, impregnating solution and catalyst are similar to those of example 5.

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 hours Then at sulpicianus catalyst serves the flow of hydrogen and straight-run diesel fuel with a sulfur content of 1.06 wt.% determine the yield of liquid oil and the sulfur contents under the following conditions by the sa: temperature 350° C, a pressure of 3.5 MPa, mass flow rate of diesel fuel 2 h-1and a volume ratio of hydrogen/diesel fuel 500.

The catalyst provides the yield of liquid oil level 96-99% and Hydrotreating diesel fuel sulfur content in it 20-32 ppm.

Example 11 (table 2)

The preparation method of the carrier, impregnating solution and catalyst are similar to those of example 8.

Conditions sulfatirovnie and testing are similar to those of example 10 (temperature 350°and the volume ratio of hydrogen/diesel fuel 500). Under these conditions, the catalyst provides the output of liquid oil at the level of 97% and a Hydrotreating diesel fuel sulfur content therein 50-75 ppm.

Example 12 (comparative prototype, table 3)

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 phosphomolybdenum acid and stirred at the same temperature until complete dissolution. The resulting solution has a pH value of 0.52, contains 24 wt.% Moo3, the molar ratio of Mo/Co 2.4 and P/Mo 0,2.

As the carrier used extrudates, obtained by extrusion of a paste based on pepsirefresh of aluminum hydroxide continuous deposition, to follow the stages of their 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 Ådefined isotherms of nitrogen adsorption. 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 catalyst contains, wt%: 21,3 of Moo3, 4,6 Soo and 1,2 R.

The catalyst after calcination at 150°has a specific surface area (Sbeats) 150 m2/g, pore volume (VΣ) 0,31 cm /g and the average radius of the pores (Dcf) 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 13 (comparative 1, table 3)

An impregnating solution is prepared analogously to example 1, but for solution preparation take 9,27 g of cobalt carbonate, of 10.21 g of citric acid monohydrate, 26,95 g of molybdenum oxide and 2.14 g of 85%phosphoric acid. The resulting solution containing 34 wt.% Moo3has a molar ratio of Mo/Co, 2.4, and P/Mo of 0.1, and has a pH of 2.4.

After impregnation 30 g of the carrier and the sample 1, containing aluminum oxide and CA-montmorillonite in a weight ratio of 85/15, with 25.5 ml of solution, the catalyst is dried and calcined under the conditions of example 1.

Textural characteristics and the composition of the catalyst are given in table 3.

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.

Example 14 (comparative 2, table 3)

Similar to example 1, but to prepare an impregnating solution using a 7.62 g of cobalt carbonate, 8,96 g of citric acid monohydrate, and 22.6 g of molybdenum oxide and 5,77 g of phosphoric acid (85%solution). The solution contains of 25.4 wt.% Moo3has a molar ratio of Mo/Co 2.4 and P/Mo 0,38, and pH of 0.75.

Textural characteristics and the composition of the catalyst are given in table 3.

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 15 (comparative 3, table 2)

The method of preparation of the medium, the composition of the impregnating solution and catalyst analogous to example 14.

When the test conditions of example 10 (at 350°and a volume ratio of hydrogen/diesel fuel 500) catalyst provides a 95% yield of liquid oil and the sulfur content in them at the level of 85-90 ppm.

Example 16 (comparative 4, table 2)

is nological example 1, but to prepare an impregnating solution using a 5.1 g of cobalt carbonate, 6.0 g of citric acid monohydrate, 18,53 g of molybdenum oxide and 7,03 g of phosphoric acid (85%solution). The solution contains of 25.4 wt.% Moo3has a molar ratio Mo/3 and R/Mo 0.4 and pH of 0.5.

Textural characteristics and the composition of the catalyst are given in table 2.

When the test conditions of example 10 (at 350°and a volume ratio of hydrogen/diesel fuel 500) catalyst provides a 97% yield of liquid oil and the sulfur content in them at the level of 120-140 ppm.

Example 17 (comparative 5, table 3)

Similar to example 1, but to prepare an impregnating solution used to 9.57 g of cobalt carbonate, of 11.26 g of citric acid monohydrate, 27,82 g of molybdenum oxide and 5,28 g of phosphoric acid (85%solution). The solution after dilution contains 34 wt.% Moo3has a molar ratio of Mo/Co 2.4 and P/Mo 0,24, pH of 0.85.

Textural characteristics and the composition of the catalyst are given in table. 3.

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 380-420 ppm at 340°C.

Example 18 (comparative 6, table 2)

To prepare an impregnating solution of 11.75 g paramolybdate ammonium (NH4)6·Mo7O24·4H2O, dissolved in 12 ml distilleria the Noi water, mixed from 4.25 g of 85%phosphoric acid (85%solution), heated to 80°C. After complete dissolution of the added 3.5 g of monohydrate citric acid and 6.5 g of cobalt nitrate, Co(NO3)2·6N2A. After dissolution receive a solution with a volume of 22 ml Solution contains a 22.4 wt.% Moo3has a molar ratio Mo/3 and R/Mo of 0.5 and a pH of 0.7.

For the preparation of the catalyst take 30 g of calcined extrudates from example 1, containing Al2About3and CA-montmorillonite in a weight ratio of 85/15. To the extrudate add 22.5 ml of a solution and are impregnated at 25°C for 15 minutes

The impregnated extrudates are dried in a stream of nitrogen and then calcined in the muffle in an atmosphere of air at 200°C for 2 hours

Textural characteristics and the composition of the catalyst are given in table 2.

When the test conditions of example 10 (at 350°and a volume ratio of hydrogen/diesel fuel 500) catalyst provides a 95% yield of liquid oil and the sulfur content in them at the level of 200-250 ppm.

Example 19 (comparative 7, table 2)

The composition and sequence of preparation of the impregnating solution are similar to those of example 5, the difference lies in the fact that for the preparation of the catalyst used, the catalyst is aluminum oxide.

For the preparation of alumina extrudates industrial use is hydrated powder of aluminum hydroxide, obtained by hydrolysis of aluminum isopropylate and having a structure of pseudoboehmite. To obtain the molding paste to 39 g Sol of aluminum hydroxide with humidity 28% add 3 ml of concentrated nitric acid (density of 1.41 g/cm3)mixed with 49 ml of distilled water, and stirred Z-shaped mixer. Next, to the obtained solu add 4.94 g of powder γ-Al2O3that stirred the mass for 20 min and molded in the form of cuttings. The extrudates drying and calcination in air stream at 550°C for 4 h the resulting extrudates have a specific surface area of 235 m2/g, pore volume of 0.51 cm3/g and an average pore 85 Ådetermined from adsorption isotherms of nitrogen. The share of pore size 70-130 Å accounts for 50% of the total pore volume.

For impregnation take 30 g of extrudates and 21 ml of impregnating solution. The conditions of drying and heat treatment are the same as those of example 1.

Textural characteristics and the composition of the catalyst are given in table 2.

When the test conditions of example 10 (at 350°and a volume ratio of hydrogen/diesel fuel 500) catalyst provides a 98% yield of liquid oil and the sulfur content in them at the level of 50-65 ppm.

It is seen that the inventive compositions of Co(Ni)-Mo catalysts containing compounds of molybdenum, cobalt(Nickel), and phosphorus in a molar ratio Mo/(Co+Ni) - 1.3 to 2.6 the P/Mo 0,08-0,1, disperision on a porous alumina carrier with modifying additive montmorillonite (examples 1-3 and 4-9)have gidroobesserivaniya activity and resistance to deactivation higher than the samples with a ratio P/Mo≥0,2 (examples 12, 14). Within these limits molar ratio Mo/Co and/or Mo/Ni and P/Mo, the content of the active component mainly in the number 16-21 wt.% Moo3and 4-6 wt.% COO and/or NiO is sufficient for use in existing installations Hydrotreating petroleum fractions, providing at a temperature of 340°C, pressure of 3.5 MPa and a ratio of hydrogen/fuel 300 hydrotreatment of diesel fuel from the sulfur compounds to sulfur content not higher than 300 ppm. Under similar conditions hydrodesulphurization unit samples characterized by high content of phosphorus (P/Mo≥0,2, examples 12, 14)enables the removal of sulfur from diesel fuel only to the level of 380-420 ppm.

It is seen that at the close oxide content molybdene (for example, 19 wt.%) increasing the molar ratio of Mo/Co and/or Mo/Ni in the catalyst above 2.4, for example to 2.6 (example 4) or 3.0 (example 16), leads to a decrease gidroobesserivaniya the activity of the catalyst. So, Co-Mo catalysts with content of 19 wt.% Moo3and the ratio of Mo/Co, is equal to 2.0 (example 1) and 2.6 (example 4), provide the hydrodesulphurization unit of diesel fuel to the content of the sulfur level 150-180 and 370 ppm, respectively, at a temperature of 340°C, pressure of 3.5 MPa and a ratio of hydrogen/fuel 300. The tendency to decrease gidroobesserivaniya activity of the catalysts, which is characterized by a molar ratio Mo/From above 2.4, is observed during the process hydrodesulphurization unit at a temperature of 350°and higher volumetric ratio of hydrogen/fuel 500 (example 16).

The tendency to decrease gidroobesserivaniya activity of Co-Mo catalysts is observed with decreasing molar ratio of Mo/Co and/or Mo/Ni below 1.4, but in this case, the decrease of activity is not as strong. So, Co-Mo catalysts with content of 19 wt.% Moo3and the ratio of Mo/Co, is equal to 2.0 (example 1) and 1.4 (example 2)at a temperature of 340°To provide a hydrodesulphurization unit diesel fuel sulfur level 150-180 and 210-230 ppm, respectively.

The tendency to decrease of catalytic activity in the process hydrodesulphurization unit diesel fuels is observed with increase in the content of molybdenum oxide to 29 wt.% (example 13). However, this trend is weaker in the introduction of cobalt and phosphorus in the claimed limits of the molar ratios of P/Mo and Mo/Co, as can be seen from a comparison of the activity of the samples of examples 13 and 17, providing diesel hydrodesulphurization unit fractions to the level of 360-380 ppm and 380-420 ppm, respectively.

Comparison of the activity of samples 16 and 18, have their similar chemical composition, shows that the use as precursors of active compounds of molybdenum oxide and cobalt carbonate (example 16) is preferred since it provides the catalyst for most gidroobesserivaniya activity compared with the catalyst prepared from an impregnating solution containing paramolybdate ammonium and nitrate cobalt (example 18). At a temperature of 350°and a ratio of hydrogen/fuel 500 sample 16 and 18 provide a sulfur content in diesel fuel at the level of 120-140 and 200-250 ppm, respectively.

The reduction of the content of phosphate ion in the catalyst on the ratio P/Mo, 0.2, 0.08, and 0.1 allows to increase the stability of the catalyst to deactivation, as is shown by experiments on the effects of high temperature process for hydrotreatment of diesel fractions. So, after exposure to a temperature of 370°C for 7-9 h samples with close content molybdenum oxide, characterized by a molar ratio of P/Mo in the claimed limit of 0.08-0.1 (example 5) and a ratio R/Mo≥0.2 (example 14), provide the hydrodesulphurization unit diesel fuels to the level of 330-350 and 440-450 ppm, respectively.

Activity comparison of samples No. 5 and 19, having a similar composition of the active component, shows that the introduction of additives montmorillonite to the aluminum oxide has a positive effect on g is groovesalad activity. Samples No. 5 and 19 prepared on alumina carriers with the addition of montmorillonite and without it, provide a Hydrotreating of diesel fuel to the level 19-32 and 50-65 ppm, respectively, at a temperature of 350°and the frequency of circulation of the hydrogen-containing gas 500. The introduction of the alumina carrier additives montmorillonite provides the media with a developed porous structure (not less than 0.6 cm3/g) with a narrow distribution of pore sizes (mostly with pores 80-140 Å), the optimum acidity and high mechanical strength. In addition, the presence of montmorillonite 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, both due to the increasing acidity of the medium, and due to the presence of montmorillonite cations CA and Mg.

The inventive catalyst composition provides improved gidroobesserivaniya activity of Co(Ni)-Mo catalyst at moderate temperatures (320-340° (C) and pressures (up to 3.5 MPa) their use with a simultaneous increase in the stability of the catalysts for the decontamination of sulfur organic compounds at elevated temperatures (360-370° (C) and decontamination with hydrogen sulfide formed by the reaction of the hydrogenolysis of organic sulfur is of such compounds.

Table 1

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 2 h-1and a volume ratio of hydrogen/diesel fuel 300.
No.Chemical composition, wt.%Textural characteristicsCatalytic properties
Soo wt.%NiO wt.%Moo3wt.%P wt.%Mo/Co(Ni)molarP/Mo molarSbeatsm2/gVΣcm3/gDcfthat ÅDcp±15 Å, %Sulfur content, ppmXS, %Y %
340°370°340°
1.4.9-19.00.42.00.101560.339565 150-18070-80230-25098.6 98.396-97
2.6.9-19.00.331.430.081440.319065210-23035-55295-31098.0-97.896
3.3.8-17.50.412.400.111390.339565220-25070-90295-31097.9-97.697
4.3.6-18.00.352.600.091580.3393633706040096.597
5.4.4-21.10.452.400.101200.308760250-28045-55330-35097.697.496
6.5.4-21.60.372.080.081200.3096 60280-30050-60370-39097.4-97.196
7.5.4-21.60.382.080.081150.319862280-30040-50360-37097.4-97.196
8.4.3-17.20.382.080.101380.297554240-27040-50290-33097.7-97.496
9.3.91.220.30.412.070.091480.349058250-29070-90330 to 34097.7-97.396
Texture features derived from the adsorption isotherms of nitrogen: Sbeatsthat is, m2/g specific surface area by BET; VΣcm3/g pore volume, desorption isotherms of nitrogen; Dcpthat Å average pore; Dcp±15 Å, % - proportion of pores with a size of Dcp±15 Å;
Catalytic characteristics: sulfur content in liquid nafter the products, ppm, when the above process temperatures; XS, % - degree hydrodesulphurization unit at 340°S; Y, % yield of liquid oil at 340°C;

99.7
Table 2

The chemical composition and textural characteristics of the catalysts and their catalytic properties defined in the Hydrotreating process of straight-run diesel fuel at a temperature of 350°C, a pressure of 3.5 MPa, the fuel 2 h-1and a volume ratio of hydrogen/diesel fuel 500.
No.Chemical composition, wt.%Textural characteristicsCatalytic characteristics at 350°
Soo, wt.%NiO,

wt.%
Moo3,

wt.%
P, wt.%Mo/Co(Ni)molarP/Mo molarSbeatsm2/gVΣcm3/gDcfthat ÅDcf±15 Å, %Sulfur content, ppmXS, %Y%
104.4-21.10.452.400.101200.30876019-3296-99
114.317.20.382.080.101380.29755450-7599.397
154.73-20.81.392.290.311100.24964585-9099.195
163.28-19.21.593.000.381050.249050120-14098.797
182.87-16.21.652.940.471010.239240200-25097.695
193.6-17.40.372.400.101370.24676050-6599.498
Texture features derived from the adsorption isotherms of nitrogen: Sbeatsthat is, m2/g - unit power is the ability to BET; VΣcm3/g pore volume, desorption isotherms of nitrogen; Dcpthat 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, at a temperature of 350°C; XS, % - degree hydrodesulphurization unit at 350°S; Y, % yield of liquid oil at 350°C;

Table 3

The chemical composition and textural characteristics of the comparative samples 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 2 h-1and a volume ratio of hydrogen/diesel fuel 300.
No.Chemical composition, wt.%Textural characteristicsCatalytic properties
Soo, wt.%NiO, wt.%Moo3,wt.%P,

Wt.%
Mo/Co(Ni)molarP/Mo molarSbeatsm2/gVΣcm3/gDcpthatÅ Dcf±15 Å, %Sulfur content, pmmXS, %Y%
340°370°340°
12.4.6-21.31.22.40.261500.318550380-40085-90440-45096.4 96.296
13.5.7-26.40.622.400.11940.238050360-38085-90415-43096.6 96.496
14.4.73-20.81.392.290.311100.249645380-40055-60440-45096.4 96.296
17.5.85-27.01.742.400.3810.217545380-42055-60440-48096.4 96.096
Texture features derived from the adsorption isotherms of nitrogen: Sbeatsthat is, m2/g specific surface area by BET; VΣcm3/g pore volume, desorption isotherms of nitrogen; Dcpthat 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 hydrodesulphurization unit at 340°S; Y, % yield of liquid oil at 340°C;

1. The catalyst for processes of diesel hydrodesulphurization unit fractions, including active component metal oxides VIII and VIB groups and phosphorus dispersed on the alumina carrier, characterized in that as the carrier, it contains a composition of aluminum oxide and montmorillonite in the following ratio, wt.%: montmorillonite 5-15, aluminum oxide, 85-95; as an active ingredient contains, wt%: molybdenum oxide of Moo314,0-29,0, cobalt oxide COO and/or Nickel oxide 3-8, phosphorus of 0.1-0.5, the media and the rest at a molar ratio Mo/Co and/or Mo/Ni 1.3 to 2.6 and P/Mo 0,08-0,1.

2. The catalyst according to claim 1, characterized in that the medium contains CA - or Na-form of montmorillonite.

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

4. SPO is about receiving 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 dispersed in water montmorillonite with humidity 55-70% in the amount of 5-15 wt.% in the calculation of the finished product, forming by extrusion, drying and calcination at 500 to 600°; and provides media specific surface area of 200-300 m2/g, pore volume of 0.5-0.9 cm3/g, predominant pore 80-120 Å.

5. The method according to claim 4, characterized in that the weight on the basis of aluminum hydroxide and montmorillonite enter peptisers additive monobasic acid: nitric or acetic acid, in an amount to provide a molar ratio of acid/Al2O3in the range 0.001-0.07 respectively.

6. The method according to claim 4, characterized in that as montmorillonite use CA - or Na-form of montmorillonite.

7. A method of producing a catalyst for processes of diesel hydrodesulphurization unit fractions, including impregnation of calcined alumina carrier complex solution of salts of metals of the VIII and VI groups of the Periodic system and phosphorus followed by 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 montmorillonite content, wt.%: montmorillonite 5-15, aluminum oxide 85-95, the impregnating solution contains molybdenum oxide and cobalt carbonate and/or the El at a molar ratio Mo/Co and/or Mo/Ni, equal to 1.3 to 2.6, stable phosphoric acid and citric acid to the molar ratio P/Mo within 0,08-0,1, and pH in the range of 1.3 to 3.5.

8. 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 claim 7.

9. The method of claim 8, 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 2 h-1, the volumetric ratio of hydrogen/fuel 300-500.



 

Same patents:

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: petroleum processing and petrochemistry.

SUBSTANCE: catalytic system is prepared by consecutively charging into reactor alumino-cobalt and alumino-nickel-molybdenum catalysts containing 12.0-25.0% molybdenum oxide, 3,0-6.0% nickel oxide, and 3.0-6.9% cobalt oxide provided that alumino-cobalt and alumino-nickel-molybdenum catalysts are charged at ratio between 1.0:0.1 and 0.1:1.0, preparation of catalysts employs mixture of aluminum hydroxide and/or oxide powders, to which acids are added to pH 1-5. More specifically, aluminum hydroxide powder mixture utilized is a product of thermochemical activation of gibbsite and pseudoboehmite AlOOH and content of pseudoboehmite in mixture is at least 70%, and aluminum oxide powder mixture utilized comprises powders of γ-Al2O3 with particle size up to 50 μm and up to 50-200 μm taken at ratio from 5:1 to 2:5, or γ-Al2O3 powders with particle size up to 50 μm, 50-200 μm, and up to 200-400 μm taken at ratio between 1:8:1 and 3:6:1.

EFFECT: method of preparing catalytic systems for large-scale high-sulfur hydrocarbon feedstock hydrofining processes is provided allowing production of products with desired levels of residual sulfur and polycyclic aromatic hydrocarbons.

4 tbl, 3 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention provides catalyst for hydrofining of petroleum fractions, which catalyst shows elevated strength and stability upon regeneration. This is achieved supplementing alumina-based carrier with texturing additives selected from alumina and gibbsite thermochemical activation product in amount 5 to 30 wt %. Alumina additive is used with particle size not larger than 15 μm and gibbsite thermochemical activation product with that not larger than 45 μm. As binding agent in catalyst, nitric acid is used at molar ratio to alumina (0.01-0.03):1 and/or aluminum nitrate/ aluminum metal reaction product in amounts 1 to 5% based on alumina. Prior to be impregnated, catalyst is steamed at elevated temperature and impregnation is carried out from aqueous solution of nickel-cobalt-molybdenum-containing complex at pH 1-3.

EFFECT: improved performance characteristics of catalyst.

2 cl, 3 tbl, 10 ex

FIELD: petroleum refining industry.

SUBSTANCE: the invention is pertaining to the field of petroleum refining industry, in particular, to the methods of production of an ecologically pure diesel fuel. Substance: carry out hydraulic purification of a mixture of a virgin diesel fraction and distillate of carbonization and a catalytic cracking. The layers of the catalysts are located in the following way. The first on a course of traffic of a gas-raw material stream protective layer of wide-porous low-percentageNi-Co-Mo/Al2O3 catalyst is made in the form of the hollow cylinders. The second layer - the catalyst with a diameter of granules of 4.5-5.0 mm. The third - the basic catalyst made in the form of granules with a diameter of 2.0-2.8 mm. The basic catalyst has a surface of 250-290 m2 /g, a pore volume - 0.45-0.6 cm3 / g, in which - no less than 80 % of poremetric volume is formed by the through internal pores predominary of a cylindrical shape with a diameter of 4.0-14.0 nanometers. The last layer on a course of raw material traffic layer is organized analogously to the second layer. Loading of 2-4 layers is performed by a method of a tight packing. The technical result - production of the diesel fuel with improved ecological performances and with a share of sulfur less than 350 ppm from the mixture of the virgin run fraction and distillates of a carbonization and a catalytic cracking containing up to 1.3 % mass of sulfur, at a low hardness of the process and a long time interrecovery cycle.

EFFECT: the invention ensures production of the diesel fuel with improved ecological performances and with a share of sulfur less than 350 ppm.

7 cl, 2 tbl, 2 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: chemical industry; methods of preparation of the platinum hydrophobic catalyst used for separation of the isotopes of hydrogen and water.

SUBSTANCE: the invention is pertaining to the methods of preparation of the platinum hydrophobic catalyst used for separation of the isotopes of hydrogen in the columns of the isotope exchange of hydrogen with water. According to the offered method platinum is deposited at the room temperature from the solution of hexachloroplatinum acid H2PtCl6·6H2O in the mixed solvent (the mixture of acetone and mesityl oxide containing 10÷90 vol. of % of mesityl) on the hydrophobic spherical granules of the copolymer of styrene with divinylbenzene (DVB), in which the contents of paradivinylbenzene is no more than 15 mass %, the total contents of the all forms of DVB makes 10-70 mass %, and the mean size of the pores in the granules of the carrier is no less than 300 Å. After ageingin the impregnating solution the carrier is dried and restored with the help of hydrogen. 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). At that the quantity of platinum makes 0.4-1.0 mass %, and the size of the spherical granules lays in the interval of 0.5÷1.0 mm.

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: 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

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