RU2691650C1 - Cracking catalyst for heavy oil residues, viscous and high viscous oil - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: invention relates to chemical technology of producing cracking catalysts of heavy oil residues, viscous and high viscous oil. Described is a catalyst for cracking heavy oil residues, viscous and high viscous oil, heavy and super heavy oil feedstock, which includes a carrier, a hydrogenating component selected as one or more metals from the group: nickel, cobalt, molybdenum, tungsten, wherein the carrier is a highly porous cellular support from a metal selected from: nickel, chromium, copper, iron, titanium, aluminum in an individual form or in combinations with each other, or from aluminum oxide, of iron oxide or in combination with each other; carrier is characterized by porosity of not less than 85 %, average size of pores (cells) of 0.5–6.0 mm; on a highly porous cellular support there is a layer of a secondary carrier selected from: zeolite, aluminum oxide, iron oxide, silicon oxide, titanium oxide, zirconium oxide, aluminosilicate, iron silicate, clay or any combination thereof; secondary carrier is characterized by thickness from 10 to 2,000 mcm, specific surface area of not less than 20 m/g, pore volume from 0.1 to 1.0 cm/g, wherein pores with diameter greater than 5 nm are not less than 50 % of total pore volume; secondary carrier is characterized by the presence of Bronsted and Lewis acid centres, wherein according to temperature-programmed desorption of ammonia, the number of medium and strong acid centres of Bronsted and Lewis with temperature ranges of ammonia desorption of 250–350 °C and more than 350 °C is 1–1,500 and 1–1,500 mcmol/g, respectively, and ratio of medium and strong acid centres of Bronsted and Lewis is 1–10:1–5; modifying element is placed either on the main carrier, or on the secondary carrier, or on both carriers; secondary carrier in total catalyst composition is not less than 5 wt%, with the following ratio of components, wt%: secondary carrier 5.0–40.0; modifying element 0–40.0; highly porous cellular carrier – balance.EFFECT: high activity of the cracking catalyst, duration of its inter-regeneration period, improved mass transfer, high efficiency of cracking.1 cl, 7 ex, 2 tbl

Description

The present invention relates to chemical technology for the production of catalysts, in particular catalysts for cracking heavy residues of oil, viscous and high-viscosity oil.

Currently, there is a deterioration in the quality of residual proven oil reserves. The share of so-called hard-to-recover reserves is large, which account for at least 55–58% of Russia's proven reserves.

One of the potential sources of oil production is viscous oil. At the same time, viscous oil reserves will increase with exploration, in particular, in the Arctic region.

The main difficulties of using this oil are the complexity of its transportation after extraction. This is due to the fact that after extracting this oil to the surface, degassing and reducing the temperature to 25 ° C, its viscosity becomes so high that the oil stops flowing.

Therefore, it is urgent to develop technologies that allow to reduce the viscosity of oil produced directly in the fields for subsequent transportation to refineries. In addition, it is important to develop technologies that make it possible to involve heavy and superheavy residues of crude oil, including residues of vacuum distillation, in oil refining. At the same time, variations of the used catalyst and technological conditions of the process can provide targeted:

- formation of the necessary ratio of distillates, group composition and yield of a certain class of hydrocarbons in the treated oil and heavy residues;

- removal of sulfur-containing compounds and impurities of heavy metals.

Currently, two approaches are used for the processing of viscous oil, heavy and extra heavy oil feedstocks.

The first is to remove excess carbon. This includes the processes of coking, thermal and catalytic cracking, visbreaking.

The second is the introduction of additional hydrogen in the hydrocarbon feedstock. These are hydro treatment processes. They can significantly increase the yield of light distillates, but they require significant amounts of hydrogen, significant investments and therefore are cost-effective.

The processes of coking, thermal and catalytic cracking, visbreaking are less complex in technological design and therefore have found greater distribution. In this case, the cracking of viscous oil, heavy and super heavy oil feedstock is carried out mainly on microspheric catalysts.

Known catalyst according to the patent of the Russian Federation No. 2427424 "Composition of catalysis intended for the processing of heavy raw materials", IPC B01J 37/04, B01J 21/16, B01J 21/06, B01J 29/80, B01J 21/12, C10G 11/02 , with priority from 10.03.2006, published on 09.03.2007. The method of obtaining a modified zeolite catalyst includes forming a suspension containing from 15 to 55 mass% of a matrix component selected from the group consisting of clays, a synthetic matrix other than columnar clay, and mixtures thereof, and from 10 to 20 mass% of a binder sol or gel , selected from the group consisting of oxides of aluminum, silicon and their mixtures, and from 0 to 15 wt.% oxide of a metal of group IVB or VB, adding here from 10 to 75 wt.% of a mixture of zeolites selected from the group consisting of:

(i) alkaline-treated selective zeolite having a structure whose ratio of silica to alumina is less than 45, and the BET method's specific surface area of pores in the range from mesopores to large pores exceeds 50 m ² / g;

(ii) an olefin selective zeolite having a structure in which the ratio of silica and alumina is less than 70;

(iii) a beta zeolite having a structure whose ratio of silicon dioxide and aluminum is less than 100;

(iv) a zeolite of the Y-faujasite type, having a structure in which the ratio of silica and alumina is less than 30;

where one or more of the above zeolites were subjected to one or more of the following treatments,

(a) impregnating the above zeolite with a phosphorus compound with the introduction of from 0.2 to 15 mass%, in terms of P ₂ O ₅ and when calculating the weight of the zeolite and either simultaneous or sequential treatment of the impregnated zeolite with water vapor or water at a temperature ranging from 110 to 800 ° C at a pressure in the range from 103.3 kPa to 6.89⋅10 ³ kPa for 0.1 to 20 hours;

(b) treating the above-mentioned zeolite Cr and / or Mn with the introduction of from 0.1 to 10 mass% of the metal, based on the weight of the zeolite;

(c) forming particles of said catalyst having a size in the range of 0.001 to 0.8 mm.

The use of catalysts ensures the production of an increased amount of light olefins when cracking heavy feedstock while simultaneously reducing the coking of the catalyst. However, the disadvantage of this catalyst is a multi-stage procedure for its preparation.

The catalyst is also known (Patent of Russian Federation No. 2624864 “Method for processing of fuel oil and heavy oil feedstock into distillate fractions”, IPC C10G 11/02, B01J 23/75, B01J 23/94, priority from 09/21/2016, published 10.07.2017) for processes of catalytic cracking of fuel oil and heavy oil feedstock, aimed at increasing the yield of light fractions. As a catalyst, cobalt powder of micron and submicron sizes is used in the amount of 0.4-0.8% by weight; the process is carried out at a temperature of 420 ° C for 1.5 h with the possibility of catalyst reuse. The technical result according to the invention is to achieve a higher conversion of fuel oil and heavy crude oil with the output of light fractions of more than 60-70% (over 60% of fuel oil and up to 96% on oil). The disadvantage of this catalyst is the use of magnetic separation for its separation from the reaction mixture.

The closest analogue is the catalyst of Russian Federation patent No. 2183503 “Catalyst and method for cracking heavy oil fractions”, IPC B01J29 / 24, B01J29 / 26, C10G11 / 05, C10G47 / 16, priority from 09/21/2000, published on 20.06.2002. The catalyst contains a zeolite selected from the group: pentasil, zeolite-beta, aluminophosphate, mordenite, silicoaluminophosphate. The high-silica zeolite is modified by polyvalent elements with a molar ratio of SiO ₂ / Al ₂ O ₃ (mol / mol) 12-150 and a Na ₂ O content of not more than 0.5 mass%. As a hydrogenating component, one or more metals selected from the group are used: nickel, cobalt, molybdenum, tungsten, boron oxide (B ₂ O ₃ ), zirconium oxide (ZrO ₂ ), or a mixture of them are used as fillers, as a binder aluminum oxide (Al ₂ O ₃ ), crystalline silica (SiO ₂ ), synthetic aluminosilicate, clay, or their mixture, and one or more elements selected from the group: Ni, Al, Ce, Fe, as modifying polyvalent elements CR, rare earths, at the following ratio uu components, wt%:

Zeolite 30-60 Hydrogenating components 15-40 Fillers 1-4 Binder component The rest is up to 100

However, this catalyst has low values of pore size, total pore volume, which does not allow for efficient mass transfer and diffusion of large molecules of heavy and super heavy oil feedstock. In addition, the pores of this catalyst are subjected to accelerated blocking and clogging of carbonaceous deposits. This leads to a decrease in the availability of active centers in the volume of a catalyst granule and a subsequent decrease in its activity.

The task of the invention is to increase the activity of the cracking catalyst, increase the duration of its inter-regeneration period of work and improve mass transfer, increase the efficiency of cracking.

EFFECT: improved diffusion characteristics, exclusion of diffuse restrictions of transport of initial compounds and reaction products, blocking of pores with carbon deposits, high cracking rate of viscous oil molecules, heavy and super heavy oil feedstock with high yield of oil components and low gas phase formation rate.

The problem is solved and the technical result is implemented by the development of a catalyst for cracking heavy oil residues, viscous and high-viscosity oil, heavy and super heavy oil feedstock, including a carrier, a hydrogenating component, for which one or several metals from the group are chosen: nickel, cobalt, molybdenum, tungsten.

The difference of the invention from the prototype is the following:

- as a carrier, a highly porous cellular carrier is taken from a metal selected from the series: nickel, chromium, copper, iron, titanium, aluminum in individual form or in combinations with each other, or from alumina, from iron oxide or in combination with each other ;

- the carrier is characterized by a porosity of at least 85%, an average pore size (cells) of 0.5-6.0 mm;

- on a highly porous cellular carrier, a layer of secondary carrier is selected, selected from the series: zeolite, aluminum oxide, iron oxide, silicon oxide, titanium oxide, zirconium oxide, aluminum silicate, ferrous silicate, clay, or any combination thereof.

- the secondary carrier is characterized by a thickness of from 10 μm to 2000 μm, a specific surface area of at least 20 m ² / g, a pore volume of 0.1 to 1.0 cm / g, in which pores with a diameter of more than 5 nm constitute at least 50% of the total volume since;

- secondary carrier is characterized by the presence of Brønsted and Lewis acid centers, according to the data of temperature-programmed desorption of ammonia, the number of medium and strong acid centers of Brønsted and Lewis with ammonia desorption temperature ranges of 250-350 ° С and more than 350 ° С is 1-1500 and 1 -1500 µmol / g, respectively, and the ratio of medium and strong acid centers of Brønsted and Lewis is 1-10: 1-5.

- the modifying element is placed either on the primary carrier, or on the secondary carrier, or on both carriers;

- secondary carrier in the total composition of the catalyst is not less than 5 mass% in the following ratio of components, mass. %:

Secondary media 5.0 - 40.0 Modifying element 0 - 40, Cellular carrier rest.

With the specified set of restrictive and distinctive features:

- highly porous cellular carrier, characterized by a porosity of at least 85% and an average pore size (cell) of 0.5-6.0 mm, provides high mass and heat transfer, low hydraulic resistance, no diffusion limitations of the reaction molecules;

- the presence of a secondary carrier with a thickness of from 10 μm to 2000 μm, with a specific surface of at least 20 m ² / g, a pore volume of from 0.1 to 1.0 cm ³ / g, in which pores with a diameter of more than 5 nm are at least 50% total pore volume, with a content of at least 5 mass%, ensures the absence of diffusion restrictions on the access of reactive molecules to active sites, which leads to an increase in catalyst activity and the duration of the period between regeneration;

- the presence of medium and strong acid centers of Brønsted and Lewis on the surface of the secondary carrier with temperature ranges of ammonia desorption of 250-350 ° C and more than 350 ° C in the amount of 1-1500 and 1-1500 µmol / g, respectively, with the ratio of medium and strong acid centers Bronsted and Lewis 1-10: 1-5 provides a high rate of cracking of molecules of viscous oil, heavy and super heavy oil feedstock with a high yield of oil components and a low rate of formation of hydrocarbon deposits and gas phase hydrocarbons; regulation of the number and ratio of acid centers is carried out by the number of starting compounds and temperature treatments;

- the presence of the modifying element determines the optimal properties of the active centers with high activity in cracking reactions. From the given series of modifying elements, some elements lead to an increase in the strength of highly porous permeable cellular carrier, optimize its surface properties for more efficient fixing of the secondary carrier. The application of these elements to the secondary carrier leads to an optimization of the concentration and strength of the surface active centers. Some modifying components function as binders — Mg, Ce, Ti, Zr, Si.

The acid centers of Bronsted and Lewis exist on any surface of inorganic oxides. The Bronsted center is the protons (H ⁺ ) in the composition of the hydroxyl groups (-OH), the latter are associated with surface cations. The center of Lewis is coordination-unsaturated cations. This number of centers and their ratio provides the optimal rate of processing of large hydrocarbon molecules of resins and asphaltenes into hydrocarbon oils. At the same time, side reactions proceed slowly, that is, large molecules of resins and asphaltenes are converted into by-products — hydrocarbon deposits and hydrocarbons of the gas phase at low speed. If you go beyond these ranges, then in the case of a low number of Lewis and Brønsted acid centers and / or a high concentration ratio of medium to strong centers, the target reaction will proceed very slowly, and if they are high and / or a low ratio of concentration of medium to strong centers, reactions will proceed very intensively.

As a result of using a catalyst based on a highly porous carrier with a thin layer of secondary carrier in accordance with this invention, the process of cracking viscous oil, heavy and super heavy oil feedstock is carried out more efficiently, which is reflected in a significant decrease in viscosity, an increase in the yield of target hydrocarbons that make up the oils and fractions with a boiling point below 350 ° C, reducing the occurrence of side processes of the formation of light hydrocarbons, which enter the gas phase.

Known catalyst for the selective hydrogenation of acetylene and diene hydrocarbons in C ₂ -C ₅₊ -hydrocarbon fractions using primary and secondary media (RF patent №2547258). Its use also provides improved heat and mass transfer and diffusion characteristics of selective hydrogenation. In the proposed catalyst, the secondary carrier is characterized by the presence of medium and strong acid centers of Bronsted and Lewis with an ammonia desorption temperature range of 250-350 ° C and more than 350 ° C in an amount of 1-1500 and 1-1500 µmol / g, respectively, with a ratio of medium to strong acidic Brønsted and Lewis centers 1-10: 1-5 to ensure a high rate of cracking of viscous oil molecules, heavy and super heavy oil feedstock with a high yield of oil components and a low formation rate of hydrocarbon deposits and gas hydrocarbons th phase, is that both the sign and the result obtained due to its use of the prior art are not known. The secondary carrier can be selected from a wider list of compounds.

The catalyst was prepared as follows.

A highly porous metal carrier was obtained by the method of electrochemical metal deposition on a metallized substrate of a reticulated mesh-cellular polyurethane foam matrix or by a slip method.

Electrochemical deposition of metal on a metallized substrate of a reticulated mesh-cellular polyurethane foam matrix was carried out in three stages: the application of an electrically conductive layer on a polyurethane foam matrix, electrochemical deposition of a metallic coating on a metallized polyurethane foam matrix and the removal of an organic polyurethane foam matrix by styling. 8 ocloc'k.

The application of metal by slip method was carried out by duplicating the reticulated mesh-cellular polyurethane foam matrix by applying metal powders on a polyurethane foam matrix followed by a cyclic mechanical effect of compression-tension. Next, the excess slip was removed by pressing the sample to a given mass. Then successively drying the impregnated blanks at a temperature of 100-120 ° C for 1-4 hours and firing at a temperature of 1200-1900 ° C for 2-8 hours.

Nickel, chromium, copper, iron, titanium, aluminum in individual form or in combinations with each other were used as the starting metal of the highly porous carrier.

Highly porous carrier of aluminum oxide or iron oxide or their combination was obtained by slip method, which consisted in impregnation of reticulated mesh-cellular polyurethane foam matrix with solutions of aluminum compounds by cyclic compression-tension effect. Next, the excess slip was removed by pressing the sample to a given mass. Then successively drying the impregnated blanks at a temperature of 100-120 ° C for 1-4 hours and firing at a temperature of 1200-1700 ° C for 2-8 hours. At the same time, various modifications of aluminum oxide were formed (γ-A1 ₂ O ₃ , β-Al ₂ O ₃ , η-Al ₂ O ₃ , δ-Al ₂ O ₃ , θ-Al ₂ O ₃ , α-Al ₂ O ₃ ) and various modifications of iron oxide in individual form or in combination with each other.

As a starting compound for the preparation of a highly porous carrier of alumina, various salts, hydroxides, aluminum oxides were used in individual form or in combinations with each other.

As a starting compound for the preparation of a highly porous carrier of iron oxide, various salts, hydroxides, iron oxides were used in individual form or in combinations with each other.

At the same time, upon receipt of a highly porous carrier from metal, aluminum oxide or iron oxide by slip method to increase the sedimentation stability and adhesion strength while fixing the slip on the surface of the reticulated mesh-cellular polyurethane foam matrix, it is possible to add a solution of surfactant.

For the formation of a secondary layer of zeolite, aluminum oxide, iron oxide, silicon oxide, titanium oxide, zirconium oxide, silica-alumina, iron silicate, clay, or any combination thereof, the surface of highly porous metal, aluminum oxide or iron oxide was impregnated with compounds of these elements. For this, a sample of highly porous carrier was placed in the mixer chamber. Then, aqueous or organic solutions of the starting compounds of the elements were dosed. Impregnation of highly porous carrier with solutions of compounds of elements was carried out for 0.1-2 hours at a temperature of 20-80 ° C. After impregnation, the highly porous carrier was dried for 0.5-2 hours at a temperature of 30-250 ° C. For the formation of a secondary layer of zeolite, aluminum oxide, iron oxide, silicon oxide, titanium oxide, zirconium oxide, silica-alumina, ferrosilicate, clay, or any combination thereof with a thickness of not less than 10 microns and not more than 2000 microns and a total mass fraction of not less than 5 % mass of the total mass of the catalyst impregnation of highly porous media with compounds of elements was carried out one or more times with drying and / or calcining after each impregnation. Moreover, upon receipt of a secondary layer of zeolite, aluminum oxide, iron oxide, silicon oxide, titanium oxide, zirconium oxide, aluminosilicate, ferrosilicate, clay, or any combination thereof, on the surface of highly porous cellular material to increase sedimentation stability and adhesion strength when attached to the surface highly porous carrier in the aqueous solution of the compound of the element may add a solution of surfactant. Next, to transfer the deposited compound of the element to the oxide form, a highly porous cellular carrier with a compound of the element was dried and calcined. The carrier with the applied compound element was calcined at temperatures from 250 ° C to 1200 ° C for 2-8 hours to form various modifications of zeolite, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, aluminosilicate, iron silicate, clay, or any combination thereof individually or in combination with each other. The secondary layer of aluminum oxide is characterized by a thickness of from 10 μm to 2000 μm, a specific surface area of at least 20 m ² / g, a pore volume of 0.1 to 1.0 cm ³ / g, pores with a diameter of more than 5 nm, which are at least 50 % of total pore volume The secondary carrier alumina in the total catalyst composition is not less than 5% of the mass. The use of a layer of secondary alumina with a thickness of not less than 10 microns and not more than 2000 microns and a total amount of not less than 5 mass% is due to the need to form a certain amount of the active phase to transform viscous hydrocarbon hydrocarbons, heavy and extra-heavy oil residues into lighter fractions.

The catalyst may also contain additional modifying element. The modifying element is at least one of the metals selected from the group: K, Na, Mg, Zn, Cu, Re, Bi, Mn, Ba, Sn, B, Ce, Cs, Fe, Cr, Ti, Zr , Si, Ni, Co, Mo, W, rare earth elements, or any combination thereof.

The introduction of the modifying element was carried out: at the stage of synthesis of highly porous cellular material and / or application of a highly porous cellular carrier by impregnation method and / or at the stage of securing the secondary carrier on a highly porous cellular carrier and / or impregnation of a highly porous cellular carrier with fixed secondary carrier.

After applying the compound of the modifying element, the catalyst was dried at temperatures from 50 ° C to 250 ° C for 1-2 hours and calcined at temperatures from 250 ° C to 800 ° C for 2-8 hours.

Potassium hydroxide, potassium nitrate, potassium bromide, potassium sulfate, potassium sulfate, potassium sulfate, potassium carbonate, potassium phosphate, potassium chloride, potassium oxalate, organometallic complex compounds of potassium in individual form or in combinations with each other were used as the starting potassium compound.

Sodium hydroxide, sodium nitrate, sodium bromide, sodium hydrosulfuric acid, sodium sulfite, sodium sulfate, sodium carbonate, sodium phosphate, sodium chloride, sodium oxalate, organometallic complex compounds of sodium in an individual form or in combinations with each other were used as the starting compound of sodium.

As the starting magnesium compound, magnesium hydroxide, magnesium nitrate, magnesium nitrite, magnesium carbonate, magnesium phosphate, magnesium acetate, magnesium oxalate, organometallic magnesium complex compounds in individual form or in combinations with each other were used.

Zinc hydroxide, zinc sulfate, zinc nitrate, zinc phosphate, zinc chloride, zinc carbonate, zinc chromate, zinc dichromate, zinc chromite, zinc oxalate, zinc acetate, zinc acetylacetonate, organometallic complex zinc compounds in individual form or in combinations with each other.

Copper sulfate, copper hydroxide, copper nitrate, copper nitrite, copper carbonate, copper chromite, copper chromate, copper dichromate, copper acetate, copper acetylacetonate, copper complexes with polyhydric alcohols (for example, copper glycerate, etc. .) or mixtures thereof, organometallic complex compounds of copper in individual form or in combinations with each other.

Rhenium acid, rhenium chloride, rhenium bromide, rhenium sulfide, ammonium perrhenate, rhenium (IV) oxide, rhenium (VII) oxide, organometallic rhenium complex compounds in individual form or in combinations with each other were used as the starting compound of rhenium.

Bismuth nitrate, bismuth hydroxide, bismuth sulfide, bismuth dichromate, bismuth hydroxide, bismuth iodide, bismuth oxycarbonate, bismuth oxychloride, organometallic bismuth complex compounds in individual form or in combinations with each other were used as the starting bismuth compound.

As the starting compound of manganese, manganese (II) nitrate, manganese (II) chloride, manganese (II) bromide, manganese (II) sulfate, manganese (II) carbonate, manganese permanganate, organometallic complex compounds of manganese (II) in individual form or in combinations with each other.

Barium hydroxide, barium nitrate, barium bromide, barium iodide, barium hydrosulfuric acid, barium carbonate, barium sulfate, barium formate, organometallic complex barium compounds in individual form or in combinations with each other were used as the starting compound of barium.

As the starting compound of tin, tin (II) oxide, tin (IV) oxide, tin (II) hydroxide, tin (II) sulfate, tin (IV) sulfate, tin (II) chloride, tin (IV) chloride, tin sulfide were used. (II), tin (IV) sulfide, hydrogen hexachlorostannate (IV), sodium hexahydroxostannate (IV), organometallic complex tin compounds in individual form or in combinations with each other.

The starting boron compound used boron oxide trihydroxide boron, boric acid, boron fluoride, bromide, boron iodide, boron sulfide, boron boroftoristovodorodnuyu acid, sodium metaborate, sodium tetraborate, tetrafluoroborate, ammonium tetrafluoroborate potassium tetragidridoborat lithium, sodium tetragidridoborat sodium tetragidroksoborat , trifluoroammineboron, sodium tetrafluoroborate, organometallic complex boron compounds in individual form or in combinations with each other.

As the starting compound of cerium, cerium (III) oxide, cerium (IV) oxide, cerium (III) nitrate, cerium (III) sulfate, cerium (IV) sulfate, cerium (III) sulfate, cerium (III) carbonate, cerium phosphate were used (III), cerium (III) oxalate, cerium (III) acetate, cerium (III) acetylacetonate, organometallic complex compounds of cerium in individual form or in combinations with each other.

The starting compound of cesium was cesium oxide, cesium fluoride, cesium chloride, cesium bromide, cesium iodide, cesium sulfide, cesium nitrate, cesium sulfate, cesium oxalate, cesium acetate, cesium acetate, cesium acetylacetate, organometallic complex compounds of cesium in an individual form or an individual form. with a friend.

Iron (III) oxide, iron (II, III) oxide, iron (III) hydroxide, iron (III) nitrate, iron (II) sulfate, cobalt sulfate (III), iron (II) phosphate were used as the source of the initial iron compound. , iron (III) phosphate, iron (II) fluoride, iron (III) fluoride, iron (II) bromide, iron (III) bromide, iron (II) iodide, iron (II) chloride, iron (III) chloride, carbonate iron (II), iron (II) oxalate, iron (III) oxalate, iron (II) acetate, iron (III) acetylacetonate, in individual form or in combinations with each other.

Chromium nitrate, chromium sulfate, chromium phosphate, chromium oxalate, chromic acid, potassium chromate, organometallic complex compounds of chromium in individual form or in combinations with each other were used as the starting chromium compound.

The starting titanium compound used was titanium (III) oxide, titanium (IV) oxide, titanium (II) nitrate, titanium (III) fluoride, titanium (IV) fluoride, titanium (II) chloride, titanium (III) chloride, titanium chloride (IV), titanium (IV) bromide, titanium (IV) iodide, titanium (III) sulfate, titanium pyrophosphate, titanium (III) oxalate, titanium acid, organometallic complex compounds of titanium in individual form or in combinations with each other.

Zirconium hydroxide, zirconium oxide, zirconium nitrate, zirconium fluoride, zirconium chloride, zirconium bromide, zirconium iodide, zirconium sulfate, zirconium oxalate, organometallic zirconium complex compounds in individual form or in combinations with each other were used as the starting zirconium compound.

Silicon oxide, silicon hydroxide, silicic acid, silicotungstic acid, silicofluoric acid, organosilicon compounds, silicon complex compounds in individual form or in combinations with each other were used as the starting silicon compound.

Nickel hydroxide, nickel nitrate, nickel sulfate, nickel phosphate, nickel chloride, nickel carbonate, nickel oxalate, nickel acetate, nickel acetylacetonate, organometallic nickel compounds in individual form or in combinations with each other were used as the starting nickel compound.

Cobalt (II) oxide, cobalt (II, III) oxide, cobalt (III) oxide, cobalt hydroxide, cobalt (II) fluoride, cobalt bromide (II), cobalt (II) chloride, cobalt chloride (III), cobalt (II) iodide, cobalt (II) nitrate, cobalt (II) carbonate, cobalt (II) oxalate, cobalt (II) acetate, cobalt (II) acetate, cobalt (III) acetylacetonate, cobalt (II) chromate (II) ), complex compounds with a cobalt-containing anion (for example, potassium disulfate cobaltiate, sodium hexanitrocobaltiate, etc.), individually th form or in combinations with each other.

As the source of the original molybdenum compound, molybdenum (III) oxide, molybdenum oxide (IV), molybdenum oxide (V), molybdenum oxide (VI), molybdenum hydroxide (III), molybdenum bromide (II), molybdenum bromide (III), bromide were used. molybdenum (IV), molybdenum (II) chloride, molybdenum (III) chloride, molybdenum (IV) chloride, molybdenum (V) chloride, molybdenum (II) sulfide, molybdenum (III) sulfide, molybdenum sulfide (IV), molybdenum phosphate, molybdic acid, permolybdic acid, ammonium paramolybdate, molybdenum (VI) oxalate, molybdenum (II) acetate, molybdenum (VI) dioxide bis (acetyl etonat), organometallic complex compounds of molybdenum in individual form or in combinations with each other.

Tungsten oxide (IV), tungsten oxide (VI), tungsten fluoride (VI), tungsten bromide (II), tungsten bromide (V), tungsten bromide (VI), tungsten (II) chloride, tungsten (IV) chloride, tungsten (V) chloride, tungsten (VI) chloride, tungsten acid, tungsten (V) oxalate, organometallic complex tungsten compounds in individual form or in combinations with each other.

Distilled water, aqueous solutions of acetic, sulfuric, nitric, perchloric and other acids, dimethylamine, trimethylamine, propylamine, butylamine, toluene, benzene, acetonitrile, methylene chloride, ammonia solutions, chloroform, acetone were used as solvents for applying the initial compounds of the modifying element. , hydroxylamine, organic esters, alcohols or their mixtures and other solvents.

The value of the specific surface was determined by the method of low-temperature nitrogen adsorption (BET). Calculations of the porometric volume and distribution of pore volumes by the diameters of secondary aluminum oxide were carried out using the desorption branch of the isotherm according to the standard Barrett-Joyner-Highland procedure (S. Greg, C. Sing. Adsorption, specific surface area, porosity. M., Mir, 1984, 306 s .). The essence of the method for determining the parameters of the porous catalyst system is described in the method ASTM D 3663-99 “Standard method for studying the surface area and pore volume of catalysts and catalyst carriers”

The phase composition of the carrier and the catalyst was determined by the method of x-ray diffraction. Shoot radiographs were performed using _α SuK longwave radiation and graphite monochromator on the diffracted beam. The recording range of angles in the 2θ scale is from 5 to 95 degrees.

Testing of catalysts in the process of reducing the viscosity of oil is carried out in an adiabatic reactor with a fixed catalyst bed at a temperature of 350-415 ° C, atmospheric pressure, with a feed rate of 14 h ^-1 . The raw material in all experiments was oil with a kinematic viscosity of 3000 cSt (Table 2). The viscosity measurements of the original and treated oil were performed on a Brookfield DV2T instrument.

The group composition of the original and the treated oil was investigated by liquid adsorption chromatography. The original oil contains: oils (alkanes, cyclans and monoaromatic arenas) in an amount up to 49.65 wt%; resins (benzene resins (polyaromatic hydrocarbons) and alcohol-benzene (acidic) resins) - up to 40.12 mass%; and asphaltenes - up to 10.23 mass% (Table 2).

Elemental analysis of the source and processed oil was performed by the method of x-ray fluorescence analysis. The original oil contains up to 3.84% by weight of sulfur, 0.016% by weight of vanadium, 0.0038% by weight of nickel. The remaining elements identified by this method of analysis are less than 0.001% of the mass, therefore not listed in Table 2.

Thermogravimetric analysis of oil samples to determine the fractional composition was performed using the device NETZSCH TG 209 F1 Libra in the temperature range 30-800 ° С in corundum crucibles at a heating rate of 10 K min ^-1 ; Before starting the heating mode, all samples were thermostatically controlled at 30 ° C for 5 minutes. The flow of the reaction gas (nitrogen) was set at 30 ml min ^-1 , protective (nitrogen) 20 ml min ^-1 . A sample of each of the oils was measured once; the weight of the sample ranged from 4-7 mg.

Thermoprogrammed ammonia desorption to determine the concentration of Brønsted and Lewis acid sites was performed using an AutoChem 2950 HP analyzer. To do this, a sample in the amount of 0.5 g was loaded into a quartz reactor, followed by degassing in the electric furnace of the device at 550 ° C, the heating rate was 10 ° C / min. The carrier gas flow rate (He) 10 ml / min. The support was saturated with a mixture of 10% NH ₃ in He at room temperature for one hour. After that, the sample was purged with argon at 100 ° C to remove physically sorbed ammonia. Desorption spectra were recorded in the temperature range from 25–700 ° C. The determination error is ± 10%.

Indicators of heat and mass transfer were evaluated during tests of catalysts in the reaction of cracking viscous oil. The essence of the method was to measure the maximum difference in temperature along the axis of the cross section of a reactor located in the center of the catalyst layer. The diameter of the cross section of the reactor was 30 mm.

The diffusion efficiency index was estimated by the calculated value ψ - Thiele modulus. When ψ <0.5, the process goes in the kinetic region and the degree of surface utilization is close to unity, diffusion limitations are absent. When ψ> 2.5, the process proceeds in the region of internal diffusion, only a portion of the catalyst limited by the surface layer of grain is used, diffusion limitations are noted.

Table 1 shows the initial data of catalysts for catalytic tests in the process of cracking viscous oil, Table 2 presents the results of tests of these catalysts. Example 7 in Tables 1 and 2 characterizes the data of the prototype. Line 8 of Table 2 contains the crude oil figures shown for comparison.

In table 2, the amount of the gas phase characterizes the rate of occurrence of side processes of the formation of light hydrocarbons.

Examples of a specific embodiment of the invention are described below.

Example 1. The catalyst is prepared by impregnation of highly porous cellular Nickel media with a secondary layer of aluminum oxide γ-modification with an aqueous solution of cesium nitrate. Highly porous cellular nickel media is characterized by a porosity of 90%, an average pore diameter of 3.1 mm. The secondary support of the aluminum oxide γ-modification has a specific surface area of 180 m ² / g, a pore volume of 0.45 cm ³ / g, mesopores with a diameter of more than 5 nm, which together constitute 67% of the total pore volume. The thickness of the layer of aluminum oxide is 10 microns. The secondary carrier is characterized by the presence of Brønsted and Lewis acid centers, while according to the data of programmed ammonia desorption, the number of medium and strong Brønsted and Lewis acid centers with ammonia desorption temperature ranges of 250-350 ° С and more than 350 ° С is 258 and 153 μmol / g accordingly, the ratio of medium and strong acid centers of Brønsted and Lewis is 1.69: 1.0.

A highly porous cellular nickel carrier with a secondary alumina layer of γ-modification in the amount of 98.5 g is placed in the mixer chamber, and 300 ml of an aqueous solution containing 2.1992 g of cesium nitrate is metered. The impregnation is carried out for 2 hours at a temperature of impregnating solution of 60 ° C. After impregnation of a highly porous cellular nickel carrier with a secondary alumina layer of γ-modification with an aqueous solution of cesium nitrate, the solvent is removed at a temperature of 80 ° C for 3 hours. Then highly porous cellular Nickel media with a secondary layer of aluminum oxide γ-modification, impregnated with cesium nitrate, dried at 50 ° C for 2 hours and calcined to transfer cesium in the oxide state at a temperature of 600 ° C for 4 hours.

The finished catalyst is characterized by a temperature difference across the diagonal of the cross section of the catalyst layer of 0.5 ° C, and the Til module is 0.05.

The catalyst used has the following composition:

Cs - 1.5% of the mass;

γ-Al ₂ About ₃ - 6.1% of the mass;

Highly porous cellular nickel carrier - 92.4% of the mass.

The results of the catalytic tests of this sample are presented in Table 2.

Example 2. The catalyst is prepared by impregnation of highly porous cellular copper carrier with a secondary layer of aluminum oxide δ-modification and zeolite ZSM-5 with an aqueous solution of cerium nitrate. Highly porous cellular copper media is characterized by a porosity of 89%, an average pore diameter of 1.0 mm. The secondary carrier alumina δ-modification and zeolite ZSM-5 has a specific surface area of 260 m ² / g, a pore volume of 0.48 cm ³ / g, mesopores with a diameter of more than 5 nm, which together make up 78% of the total pore volume. The thickness of the aluminum oxide layer is 630 microns. The secondary carrier is characterized by the presence of Brønsted and Lewis acid centers, while according to the data of programmed ammonia desorption, the number of medium and strong Brønsted and Lewis acid centers with ammonia desorption temperature ranges of 250-350 ° С and more than 350 ° С is 300 and 1500 μmol / g accordingly, the ratio of medium and strong acid centers of Bronsted and Lewis is 1.0: 5.0.

A highly porous cellular copper carrier with a secondary layer of aluminum oxide of δ-modification and ZSM-5 zeolite in the amount of 99.95 g is placed in the mixer chamber, 200 ml of an aqueous solution containing 0.155 g of cerium nitrate are metered. Impregnation is carried out for 2 hours at a temperature of impregnating solution of 50 ° C. After impregnation of highly porous cellular copper carrier with a secondary layer of alumina of δ-modification and ZSM-5 zeolite with an aqueous solution of cerium nitrate, the solvent is removed at 80 ° C for 3 hours. Then a highly porous cellular copper carrier with a secondary layer of alumina of δ-modification and zeolite ZSM-5 impregnated with cerium nitrate is dried at 110 ° C for 2 hours and calcined at 800 ° C for 2 hours to convert cerium nitrate to oxide cerium.

The finished catalyst is characterized by a temperature difference across the diagonal of the cross section of the catalyst layer of 0.6 ° C, and the Til module is 0.11.

The catalyst used has the following composition:

Ce - 0.05% of the mass;

δ-A1 ₂ O ₃ - 3.0% of the mass;

ZSM-5 - 2.0% of the mass;

Highly porous cellular copper carrier - 94.95% of the mass.

The results of the catalytic tests of this sample are presented in Table 2.

Example 3. The catalyst is prepared by impregnation of highly porous cellular iron carrier with a secondary layer of aluminum oxide α-modification and titanium dioxide with an aqueous solution of cobalt nitrate. Highly porous cellular iron carrier is characterized by a porosity of 85% with an average pore diameter of 0.5 mm. The secondary support of aluminum oxide α-modification and titanium dioxide has a specific surface area of 20 m ² / g, a pore volume of 0.78 cm ³ / g, mesopores with a diameter of more than 5 nm, which together make up 98% of the total pore volume. The thickness of the aluminum oxide layer is 67 microns. The secondary carrier is characterized by the presence of Brønsted and Lewis acid centers, while according to the data of programmed ammonia desorption, the number of medium and strong Brnsted and Lewis acid centers with ammonia desorption temperature ranges of 250-350 ° С and more than 350 ° С is 9 and 4 μmol / g respectively, and the ratio of medium and strong acid centers of Brønsted and Lewis is 2.25: 1.0.

Highly porous cellular iron carrier with a secondary layer of aluminum oxide α-modification and titanium dioxide in the amount of 95 g is placed in the mixer chamber, 400 ml of an aqueous solution containing 24.661 g of cobalt nitrate are dosed. The impregnation is carried out for 2 hours at a temperature of impregnating solution of 60 ° C. After impregnation of highly porous cellular iron media with a secondary layer of aluminum oxide α-modification and titanium dioxide with an aqueous solution of cobalt nitrate, the solvent is removed at a temperature of 90 ° C for 1.0 hour. Then a highly porous cellular iron carrier with a secondary layer of aluminum oxide α-modification and titanium dioxide is dried at 250 ° C for 1 hour and calcined at 500 ° C for 7 hours to convert the original cobalt nitrate to cobalt oxide.

The finished catalyst is characterized by a temperature difference across the diagonal of the cross section of the catalyst layer of 0.3 ° C, and the Til module is 0.09.

The catalyst used has the following composition:

Co - 5.0% of the mass;

α-Al ₂ About ₃ - 5.0% of the mass;

TiO ₂ - 4.2% of the mass;

Highly porous cellular iron carrier - 85.8% of the mass.

The results of the catalytic tests of this sample are presented in Table 2.

Example 4. The catalyst is prepared by impregnating a highly porous cellular carrier of aluminum oxide α-modification with a secondary layer of aluminosilicate with an aqueous solution of magnesium nitrate. A-modified highly porous cellular alumina carrier is characterized by a porosity of 93% with an average pore diameter of 4.5 mm. The secondary carrier aluminosilicate has a specific surface area of 193 m ² / g, a pore volume of 0.13 cm ³ / g, mesopores with a diameter of more than 5 nm, which together constitute 50% of the total pore volume. The layer thickness of the secondary carrier is 2000 μm. The secondary carrier is characterized by the presence of Brønsted and Lewis acid centers, according to the data of temperature-programmed ammonia desorption, the number of medium and strong acid centers of Brnsted and Lewis with ammonia desorption temperature ranges of 250-350 ° С and more than 350 ° С is 1.0 and 1, 0 μmol / g, respectively, and the ratio of medium to strong acid centers of Brønsted and Lewis is 1.0: 1.0.

Highly porous cellular carrier alumina α-modification with a secondary layer of aluminosilicate in the amount of 60 g is placed in the mixer chamber, dispense 700 ml of an aqueous solution containing 426.667 g of magnesium nitrate. Impregnation is carried out for 2 hours at a temperature of impregnating solution of 40 ° C. After impregnation of a highly porous cellular carrier of aluminum oxide α-modification with a secondary layer of aluminosilicate with an aqueous solution of magnesium nitrate, the solvent is removed at 80 ° C for 1.0 hour. Then a highly porous cellular carrier of alumina α-modification with a secondary layer of aluminosilicate soaked in magnesium nitrate is dried at 110 ° C for 2 hours and calcined at 250 ° C for 4 hours to convert magnesium nitrate to magnesium oxide.

The finished catalyst is characterized by a temperature difference across the diagonal of the cross section of the catalyst layer of 0.4 ° C, Tiel's modulus - 0.23.

The catalyst used has the following composition:

Mg - 40.0% of the mass;

A1 ₂ O ₃ + SiO ₂ - 40.0% of the mass;

Highly porous cellular carrier alumina α-modification - 20.0% of the mass. The results of the catalytic tests of this sample are presented in Table 2.

Example 5. The catalyst is prepared by impregnating a highly porous cellular carrier of aluminum oxide α-modification with a secondary layer of ferrosilicate with a solution of chromium nitrate. Highly porous cellular carrier of aluminum oxide α-modification is characterized by a porosity of 90% with an average pore diameter of 6.0 mm. The secondary carrier ferric silicate has a specific surface area of 125 m ² / g, a pore volume of 1.0 cm ³ / g, and mesopores with a diameter of more than 5 nm, which together constitute 64% of the total pore volume. The thickness of the layer of aluminum oxide is 1235 microns. The secondary carrier is characterized by the presence of Brønsted and Lewis acid centers, while according to the data of programmed ammonia desorption, the number of medium and strong acid centers of Brønsted and Lewis with ammonia desorption temperature ranges of 250-350 ° С and more than 350 ° С is 95 and 9.5 mmol / g, respectively, and the ratio of medium and strong acid centers of Bronsted and Lewis is 10.0: 1.0.

Highly porous cellular carrier of aluminum oxide α-modification with a secondary layer of ferrosilicate in the amount of 98 g is placed in the mixer chamber, 200 ml of an aqueous solution containing 15.385 g of chromium nitrate is metered. The impregnation is carried out for 2 hours at a temperature of the impregnating solution of 80 ° C. After impregnation of the alumina support with an aqueous solution of chromium nitrate, the solvent is removed at a temperature of 90 ° C for 3 hours. Then alumina carrier impregnated with chromium nitrate, dried at 110 ° C for 2 hours and calcined to convert chromium nitrate to chromium oxide at a temperature of 600 ° C for 8 hours.

The finished catalyst is characterized by a temperature difference across the diagonal of the cross section of the catalyst layer of 0.4 ° C, and the Til module is 0.18.

The catalyst has the following composition:

CR - 2.0% of the mass;

Fe ₂ SiO ₄ - 7.6% of the mass;

Highly porous cellular alumina α-modification - 90.4% of the mass.

The results of the catalytic tests of this sample are presented in Table 2.

Example 6. The catalyst is a highly porous cellular alumina α-modification with a secondary layer of zirconium oxide and ferrosilicate. Highly porous cellular alumina α-modification is characterized by a porosity of 95% with an average pore diameter of 3.0 mm. The secondary support of zirconium oxide and ferrosilicate has a specific surface area of 90 m ² / g, a pore volume of 0.1 cm ³ / g, mesopores with a diameter of more than 5 nm, which together constitute 86% of the total pore volume. The thickness of the aluminum oxide layer is 600 microns. The secondary carrier is characterized by the presence of Brønsted and Lewis acid centers, while according to the data of programmed ammonia desorption, the number of medium and strong Brønsted and Lewis acid centers with ammonia desorption temperature ranges of 250-350 ° С and more than 350 ° С is 1500 and 258 μmol / g accordingly, the ratio of medium and strong acid centers of Brønsted and Lewis is 5.8: 1.0.

The finished catalyst is characterized by a temperature difference across the diagonal of the cross section of the catalyst layer of 0.3 ° C, and a Til module 0.27.

The catalyst has the following composition:

ZrO ₂ - 5.0;

Fe ₂ SiO ₄ - 4.8% of the mass;

Highly porous cellular alumina α-modification - 90.2% of the mass.

The results of the catalytic tests of this sample are presented in Table 2.

As can be seen from the above examples, the proposed catalyst is superior in activity and selectivity in cracking reactions of viscous petroleum reference catalyst - a prototype catalyst (example 7).

The activity of the catalyst determines the parameter yield of the fraction with a boiling point of up to 350 ° C. The selectivity of the catalyst determine the parameters of the oil yield and the gas phase.

The higher activity of the samples of the catalyst of this invention compared with the catalyst of the prototype due to the presence of a thin layer of secondary media. It is the presence of the secondary carrier with a thickness of 10 μm to 2000 μm, a specific surface area of at least 20 m ² / g, a pore volume of 0.1 to 1.0 cm ³ / g, in which pores with a diameter of more than 5 nm constitute at least 50% of the total pore volume, ensures the absence of diffusion restrictions on the access of reactive molecules to the active sites of the catalyst and leads to an increase in catalyst activity in reactions of cracking hydrocarbons of heavy residues of oil, viscous and highly viscous oil.

The presence of highly porous cellular carrier, characterized by a porosity of at least 85% and an average pore size (cell) of 0.5-6.0 mm, provides high mass and heat transfer, low hydraulic resistance, which also contributes to the growth of catalyst activity in cracking reactions of petroleum hydrocarbons.

The presence of medium and strong acid centers of Bronsted and Lewis with temperature ranges of ammonia desorption of 250-350 ° C and more than 350 ° C in the amount of 1-1500 and 1-1500 μmol / g, with a ratio of medium and strong acid centers of Brnsted and Lewis 1-10 : 1-5 provides a high rate of cracking of molecules of viscous oil, heavy and super heavy oil feedstock with a high yield of oil components and a low rate of formation of hydrocarbon deposits and gas phase hydrocarbons.

Claims (9)

The catalyst for cracking heavy residues of oil, viscous and high-viscous oil, heavy and super heavy oil feedstock, including a carrier, a hydrogenating component, in which one or more metals from the group are chosen: nickel, cobalt, molybdenum, tungsten, characterized in that - as a carrier, a highly porous cellular carrier is taken from a metal selected from the series: nickel, chromium, copper, iron, titanium, aluminum in individual form or in combinations with each other, or from alumina, from iron oxide or in combination with each other ; - the carrier is characterized by a porosity of at least 85%, an average pore size (cells) of 0.5-6.0 mm; - on a highly porous cellular carrier, a layer of secondary carrier is selected, selected from the series: zeolite, aluminum oxide, iron oxide, silicon oxide, titanium oxide, zirconium oxide, aluminum silicate, ferrous silicate, clay, or any combination thereof; - the secondary carrier is characterized by a thickness of from 10 to 2000 μm, a specific surface area of at least 20 m ² / g, a pore volume of 0.1 to 1.0 cm ³ / g, in which pores with a diameter of more than 5 nm constitute at least 50% of the total volume since; - secondary carrier is characterized by the presence of Brønsted and Lewis acid centers, according to the data of temperature-programmed desorption of ammonia, the number of medium and strong acid centers of Brnsted and Lewis with ammonia desorption temperature ranges of 250-350 ° С and more than 350 ° С is 1-1500 and 1 -1500 µmol / g, respectively, and the ratio of medium and strong acid centers of Brønsted and Lewis is 1-10: 1-5; - the modifying element is placed either on the primary carrier, or on the secondary carrier, or on both carriers; - secondary carrier in the total composition of the catalyst is not less than 5 wt.% in the following ratio of components, wt.%: Secondary media 5.0-4.0 Modifying element 0-40.0 Highly porous cellular carrier Rest

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