RU2717095C1 - Catalyst, method of its preparation and method of processing heavy hydrocarbon material - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to catalyst composition, method of its preparation and process of processing heavy hydrocarbon material in its presence in order to obtain oil products with high added value. Described is a catalyst for processing heavy hydrocarbon material obtained by sulphiding a composition containing an active component and a carrier, characterized in that the active component consists of a heteropoly compound containing at least one of the following compounds of the series [Co₂Mo₁₀O₃₈H₄]^6-, Co₃[PMo₁₂O₄₀]₂, Ni₃[PMo₁₂O₄₀]₂, [Co(OH)₆Mo₆O₁₈]^3-, [Ni(OH)₆Mo₆O₁₈]^2-, [Ni₂Mo₁₀O₃₈H₄]^6-, [Co(OH)₆W₆O₁₈]^3-, [PMo_nW_12-nO₄₀]^3- (where n = 1–11), [PV_nMo_12-nO₄₀]^(3+n)- (where n = 1–4), Mo₁₂O₃₀(OH)₁₀H₂[Co(H₂O)₃]₄ or a mixture thereof and an organic additive, such as citric acid, glycol or EDTA, wherein the support is aluminum oxide, silicon oxide, magnesium oxide, zeolite, aluminosilicate, porous aluminophosphate, porous silicoaluminophosphate and a combination thereof, having a regular macropore spatial structure, wherein macropore fraction with size in range from 50 nm to 15 mcm is not less than 30 % in total specific volume of pores, with specific surface area of not less than 40 m²/g with an outer surface fraction of not less than 50 % and specific pore volume of not less than 0.1 cm³/g, wherein content of cobalt catalyst calcined at 550 °C is not more than 20 wt%, nickel is not more than 20 wt%, molybdenum is not more than 20 wt%, tungsten is not more than 20 wt%, organic additive content is 5–15 wt% of catalyst weight. Method of processing heavy hydrocarbon material on described catalyst consists in passing material through fixed catalyst bed at temperature of 300–550 °C, feed rate through catalyst 0.1–2 g-raw/g-catalyst/h, in presence of hydrogen fed under pressure 7–15 MPa.

EFFECT: technical result consists in achievement of high activity (high conversion in removal of sulfur, metals, asphaltenes, heavy hydrocarbons, reduced density and viscosity, et cetera) and stability (longer service life) of catalyst under severe conditions of processing heavy hydrocarbons.

6 cl, 11 ex, 1 tbl

Description

The invention relates to the field of heavy oil refining and residual oil fractions using catalysts.

It is known that nickel and cobalt sulfides in combination with molybdenum or tungsten sulfides having different morphologies of active phase particles and deposited on a porous carrier exhibit high catalytic activity in the reactions of refining oils and petroleum products in the presence of hydrogen [RU 95105673, B01J23 / 10, 10/21/1987 ; RU 2087523, C01G45 / 08, 04/09/1993; RU 1518972, B01J23 / 10, 10.21.1987; US 4465789, B01J23 / 76, 08/14/1984].

Three main types of particle morphology of the active component are distinguished, exhibiting different catalytic activity, the so-called Me-Mo-S phases of type I, II and III [H. Topsoe, BSClaosen, NYTopsoe, P. Zeuthen // Stud. Surf Sci. Catal. 1990. V. 53. P. 77; T. Topsoe // Appl. Catal., A. 2007. V. 322. P. 3], where Me are promoters of the active Mo- or W-component - most often cobalt or nickel. Me-Mo-S phases of type I are characterized by an incomplete degree of sulfidation and the presence of Mo – O – Al bonds with the surface of the support, are often monolayer distributed over the surface of the support and exhibit low catalytic activity. In type II phases, the interaction with the carrier is much weaker, the phase has a greater degree of sulfidation, is less dispersed and consists of “multilayers” that are not associated with the carrier, and has high catalytic activity. Another highly active Me-Mo-S phase of type III includes binuclear cobalt (nickel) complexes bonded to each other with a S ₂ dimer at the edges of MoS ₂ crystallites [Y. Okamoto, K. Hioka, K. Arakawa, T. Fujikawa, T. Ebihara , T. Kubota // J. Catal. 2009. V. 268. P. 49; Y. Okamoto, A.Kato, RNUsman, T. Fujikawa, H. Koshika, I. Hiromitsu, T. Kubota J. Catal. 2009. V. 265. P. 216].

For the high activity of phases of type II and III, for example, in the breaking of C – S bonds, the promoters should be located on the “edges” of the stacks of Mo (W) S ₂ layers located on the side faces; therefore, the choice of active component precursors is important in the preparation of the catalyst. In addition, it is necessary to minimize the interaction of Co, Ni, Mo, W compounds with the surface groups of the carrier, which is also solved by the selection of precursors.

Among the possible precursors of the active phase, it is known to use heteropoly acids (HPA) and bimetallic heteropoly compounds (GPS) of a given chemical composition, structure and degree of polymerization. The patent [RU 2573561, B01J23 / 882, 01.20.2016] describes a catalyst for hydrodesulfurization of hydrocarbon feedstocks consisting of GPS containing at least one of the following heteropolyanions [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [Co (OH) ₆ Mo ₆ O ₁₈ ] ^3- , [Ni (OH) ₆ Mo ₆ O ₁₈ ] ^2- , [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [P ₂ Mo ₅ O ₂₃ ] ^6- , [PMo ₁₂ O ₄₀ ] ^3- , [SiMo ₁₂ O ₄₀ ] ^4- , [Co (OH) ₆ W ₆ O ₁₈ ] ^3- , [PW ₁₂ O ₄₀ ] ^3- , [SiW ₁₂ O ₄₀ ] ^4- , [PMo _n W _12-n O ₄₀ ] ^3- (where n = 1-11), [PV _n Mo _12-n O ₄₀ ] ^{(3 + n) -} (where n = 1-4), and an organic additive, which is a compound, containing at least one carboxyl group and 2-20 carbon atoms, while the content of the organic additive is 5-15 .% by weight of Al catalyst supported on a porous carrier (MoO ₃ content and / or WO ₃ in the calcined at 550 ° C the catalyst is 14,0-23,0% by weight of CoO and / or NiO - 4,0-6. 5 wt.%). As a cobalt compound, one of the series is used: cobalt hydroxide Co (OH) ₂ · nH ₂ O (n = 0-5), carbonic cobalt CoCO ₃ , basic carbonic cobalt CoCO ₃ · 1,5Со (ОН) ₂ ⋅nH ₂ O (n = 0.5-5.0), cobalt acetate Co (CH ₃ COO) ₂ . As a nickel compound, one of the series is used: nickel hydroxide Ni (OH) ₂ · nH ₂ O (n = 0-5), carbon dioxide nickel NiCO ₃ , basic carbon dioxide nickel NiCO ₃ · nNi (OH) ₂ ⋅mH ₂ O (n = 1-3, m = 0.5-5.0), nickel acetate Ni (CH ₃ COO) ₂ . The porous support is alumina, silica, titanium oxide, zirconium oxide, magnesium oxide, zeolite, aluminosilicate, aluminophosphate, and combinations thereof. In accordance with the invention, the catalyst in the process of hydrotreating a vacuum gas oil (fr. 350-535 ° C, density at 20 ° C 921 kg / m ³ ; sulfur content 2.07 wt.%, PAH content 10.4 wt.%) At pressure hydrogen 5.0 MPa, the ratio of hydrogen / feed 800 nl / l of raw materials, the volumetric feed rate of 1.0 h ^-1 and the temperature in the reactor 360-380 ° C provides a residual sulfur content in a stable hydrogenate in the range of 100-200 mg / kg .

Despite the fact that the described catalyst is active in the hydrotreatment of vacuum gas oil, this invention cannot be used for the processing of hydrocarbon residues (fuel oil and tar) and superheavy oil due to the rapid deactivation of the catalyst under conditions of accelerated accumulation of carbon deposits, metals and other impurities in the pores of the catalyst and block access reagents to catalytic particles.

In this technical field - the refining of heavy oils and residual oil fractions - it is well known that the texture properties of the carrier: the size, volume and distribution of pores, specific surface, are of particular importance. In the case of a small pore size (less than 50 nm), the inner surface of the catalyst becomes inaccessible to macromolecules. The task is complicated by the fact that during the processing of heavy petroleum feedstocks, the side process of the formation of coke deposits proceeds at a high speed, as a result, narrow pores are blocked, the surface falls and the catalyst is deactivated. To solve these problems, a catalyst is used with a significant proportion of large pores larger than 50 nm, which, according to the existing classification, belong to macropores.

A known method of lowering the viscosity of fuel oil by its hydroprocessing [RU 2502787, C01G45 / 08, 12/27/2013], in which fuel oil is passed through a fixed catalyst bed at a temperature of 300-600 ° C, the load on the catalyst is 0.5-2 g of fuel oil / g -kat / h, in the presence of hydrogen supplied under a pressure of 4-6 MPa at a speed of 16-80 mg-N ₂ / g-fuel oil / h. The active component of the catalyst is deposited on alumina obtained using template synthesis having an ordered spatial arrangement of macropores. Ammonium molybdate is used as a precursor to the active Mo component of the catalyst.

The patent [RU 2610525, C10G25 / 00, 02.13.2017] describes a method for deasphalting and demetallization of heavy oil feedstock, in which heavy oil or fuel oil is passed through a fixed adsorbent bed at a temperature of 300-600 ° C, the load on the adsorbent is 0.5-2 g-fuel oil / g-cat / h, in the presence of hydrogen supplied under a pressure of 4-7 MPa. The adsorbent is gamma-alumina obtained by template synthesis, containing macropores forming a regular spatial structure, and the proportion of macropores with a size in the range from 50 nm to 500 nm is at least 30% in the total specific pore volume.

The closest is a catalyst [RU 2506997, B01J23 / 74, 02.20.2014] for processing heavy oil fractions, in which the active component selected from compounds of nickel, cobalt, molybdenum, tungsten, or any combination thereof (with a cobalt content of not more than 20 wt.% , nickel - not more than 20 wt.%, molybdenum - not more than 20 wt.%, tungsten - not more than 20 wt.%), deposited on an inorganic porous carrier. As precursors of the active CoMo component, Co (NO₃)₂⋅6H₂O and (NH₄)₆(Mo₇O₂₄) ⋅4H₂O, and the precursors of the active NiW component are Ni (NO₃)₂ and H₇[P (W₂O₇)₆, the carrier consists of aluminum oxide, silicon dioxide, titanium or zirconium, aluminosilicates or iron silicates, or any combination thereof. The catalysts contain macropores forming a regular spatial structure, and the proportion of macropores larger than 50 nm is at least 30% in the total specific pore volume of the specified catalyst. To obtain a regular spatial structure of macropores, templates are used - polymer spheres with diameters from 50 to 2000 nm from polystyrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, both in the form of individual substances and their mixtures. The catalyst was tested in the reaction of hydrocracking of fuel oil and Tatar superheavy oil at a temperature of 500-600 ° C, a hydrogen pressure of 6 MPa, a feed rate of 2 g of fuel oil / g-cat / h, a hydrogen feed rate of 80 mg-N₂/ g-cut / h. As a result, it is possible to reduce the kinematic viscosity and flash point of the reaction products in comparison with the initial parameters of the raw material.

Despite the fact that the textural properties of the carriers allow one to expect high stability of the catalyst under severe conditions of heavy oil refining, the activity of these catalysts in desulfurization, demetallization, and deasphalting reactions is not high enough due to the non-optimal configuration of the active phase, in which cobalt and nickel nitrates are used as a promoter precursor, and as a precursor to the catalytically active component, (NH ₄ ) ₆ (Mo ₇ O ₂₄ ) · 4H ₂ O and H ₇ [P (W ₂ O ₇ ) ₆ ]. The preparation of these catalysts involves the deposition of these promoter compounds and the active component on a carrier and subsequent thermal treatment of the catalyst, during which compounds, for example, spinel oxide structures are formed when applied to alumina, as well as other phases that are difficult to sulfide and exhibit low catalytic activity in the hydroprocessing of hydrocarbons.

The invention solves the problem of developing a highly active and stable catalyst, a method for its preparation and a process for the processing of heavy hydrocarbons in order to obtain high added value oil products.

EFFECT: high activity (large conversion in reactions of removal of sulfur, metals, asphaltenes, heavy hydrocarbons, decrease in density and viscosity, etc.) and stability (increased service life) of the catalyst under severe conditions of processing heavy hydrocarbons.

To solve the problems of the formation of highly active phases of type I and II and the preparation of stable catalysts for the processing of heavy and superheavy hydrocarbon feeds, it is proposed to use heteropoly compounds containing both a promoter and a catalytically active component, for example, from the series [Co ₂ Mo ₁₀ as precursors of the active component O ₃₈ H ₄ ] ^6- , Co ₃ [PMo ₁₂ O ₄₀ ] ₂ , Ni ₃ [PMo ₁₂ O ₄₀ ] ₂ , [Co (OH) ₆ Mo ₆ O ₁₈ ] ^3- , [Ni (OH) ₆ Mo ₆ O ₁₈ ] ^2- , [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [Co (OH) ₆ W ₆ O ₁₈ ] ^3- , [PMo _n W _12-n O ₄₀ ] ^3- (where n = 1 -11), [PV _n Mo _12-n O ₄₀ ] ^{(3 + n) -} (where n = 1-4), Mo ₁₂ O ₃₀ (OH) ₁₀ H ₂ [Co (H ₂ O) ₃ ] ₄ or their mixture. To prevent the dissociation of hetero compounds and reduce the degree of interaction of promoters with the carrier in order to increase the depth of sulfidation of metals (Mo, Co and Ni) and the effective formation of active phases of type II and III, the combined use of GPS and organic additives in the composition of the impregnating solution is proposed. An organic additive is a compound containing at least one carboxyl group and 2-20 carbon atoms. These precursors are applied to a carrier consisting of alumina, silica, magnesium oxide, zeolite, aluminosilicate, aluminophosphate, silicoaluminophosphate, or a combination thereof having a regular spatial structure of macropores, and the proportion of macropores with a size in the range from 50 nm to 15 μm is not less than 30% of the total specific pore volume with a specific surface area of at least 40 m ² / g with an external surface fraction of at least 50% and a specific pore volume of at least 0.1 cm ³ / g. The cobalt content in the catalyst calcined in air at 550 ° C. is not more than 20 wt.%, Nickel is not more than 20 wt.%, Molybdenum is not more than 20 wt.%, Tungsten is not more than 20 wt.%.

To obtain the spatial structure of macropores, synthetic templates are used - polymer microspheres with a diameter of 50 to 2000 nm made of polystyrene (PS), methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, both in the form of individual substances and their mixtures.

To obtain the spatial structure of macropores, templates of natural origin are also used - starch, cellulose, both in the form of individual substances and their mixtures.

The spatial structure of macropores means the spatial arrangement of transport macropores, ensuring the connectivity of the macropores with each other. The specificity of the proposed method lies in the introduction of a structure-forming additive — a template — at the stage of mixing the carrier precursors and the catalyst, for example, aluminum hydroxide, alumina, pseudoboehmite, boehmite, etc. The template is then removed by burning or extraction, while the particle size and the content of the template in the initial mixture determine the properties of the micro- / meso- / macroporous structure of the resulting product, the carrier, for example, aluminum oxide. For further preparation of the catalyst, methods known in the art can be used, including impregnating a previously prepared carrier with a spatial structure of macropores with precursor compounds of the active component, or preparing mixtures of precursor compounds of the active component, carrier and templates, as well as hydrothermal treatment of these mixtures.

In accordance with the present invention, catalysts are prepared by applying the active component onto the support followed by heat treatment, wherein the carrier is impregnated with a solution of an active component precursor with the organic additive wetness or excess of solution at a temperature of 20-80 ^{° C,} dried in air at room temperature and calcined . An organic additive is a compound containing at least one carboxyl group and 2-20 carbon atoms. The carrier is alumina, silica, magnesia, zeolite, aluminosilicate, porous aluminophosphate, porous silicoaluminophosphate and their combination, with a regular spatial structure of macropores, and the proportion of macropores with a size in the range from 50 nm to 15 μm is at least 30% in the total specific pore volume with a specific surface of at least 40 m ² / g with a fraction of the outer surface of at least 50% and a specific pore volume of at least 0.1 cm ³ / g.

Method for processing a heavy hydrocarbon feedstock is carried out in the presence of a catalyst prepared by the process described above at a temperature of 300-550 ^{° C,} feed rate of feedstock through the catalyst 0.1-2 g-feed / g-catalyst / hour in the presence of hydrogen supplied at a pressure of 7 -15 MPa. As heavy hydrocarbon feedstocks, heavy oil or refinery residues such as fuel oil, tar are used.

The invention is illustrated by the following examples.

Example 1

The preparation of the catalyst includes the synthesis of a porous support template method and its impregnation with catalytically active components, followed by drying and heat treatment. As a structure-forming template, polymer microspheres, in particular polystyrene, are used as a commercial product or obtained by emulsion polymerization of styrene according to the previously described method [RU 2527573, B01J23 / 28, 09/10/2014]. As a precursor of alumina, aluminum hydroxide AlOOH of the ZAO Industrial Catalysts brand, represented by the boehmite crystalline phase (93%) with an admixture of bayerite (7%), is used.

Samples of alumina supports are prepared by adding finely divided AlOOH to the powder with a dilute solution of nitric acid (10 ^-4 M) in the presence of a dry powder of PS template with a mass content of PS template in paste of 20%. The paste is extruded to obtain granules with a diameter of 2.5 mm, a length of 5 mm The granules are dried in air for 24 hours and calcined in air at 800 ° C for 8 hours. The phase composition of the macroporous carrier after calcination is represented by a mixture of γ and δ modifications of Al ₂ O ₃ . According to nitrogen and mercury porosimetry, the specific surface area of the carrier is 140 m ² / g, the specific pore volume is 0.5 cm ³ / g, the average mesopore diameter is 15 nm, the macropores are 90 nm, the specific volume of macropores is 30% of the total specific volume then, the proportion of the outer surface is 80%.

Then the granules are impregnated with a solution of HPA H ₆ [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] and citric acid; for this, weighed portions of the reagents are placed in an aqueous solution of citric acid with the ratio Co: Mo: citric acid = 1: 5: 1.2, the pH of the solution is in the range of 3.0-4.0, the impregnation is carried out according to the moisture capacity of the carrier at a temperature of 20 ° C. After that, the granules are dried in air for 24 hours at room temperature and calcined at 120 ° C for 8 hours.

After calcination at 550 ° C, the granules contain cobalt 2 wt.%, Molybdenum - 16 wt.%.

The catalysts in an amount of 10 g are loaded into a Berti reactor, sulfidation of the active component at 420 ° C with a solution of dimethyl disulfide in benzene with a 1.5-fold stoichiometric excess of sulfur relative to the sum of metals (Co + Mo) is carried out, and then they are tested in the hydrotreatment reactions of M-100 fuel oil (sulfur content - 2.53 wt.%, density at 20 ° С - 957.9 kg / m ³ ) at a temperature of 300 ° C, pressure 7 MPa. The feed rate of the M-100 fuel oil is 0.1 g of fuel oil / g-cat / h.

The test results are shown in the table.

Example 2

The preparation of the carrier is carried out by the method described in example 1, while porous zeolite-like aluminophosphate up to 20 wt.% Is added to the paste. According to nitrogen and mercury porosimetry, the specific surface of the obtained carrier is 120 m ² / g, the specific pore volume is 0.35 cm ³ / g, the average micropore diameter is 0.6 nm, mesopore is 11 nm, macropore is 90 nm, and specific volume macropores make up 40% of the total specific pore volume, the external surface fraction is 70%.

The granules are impregnated with a solution of the heteropoly compound Co ₃ [PMo ₁₂ O ₄₀ ] ₂ and glycol, for this a weighed portion of GPS is placed in an aqueous glycol solution with the ratio Co: Mo: glycol = 1: 6.5: 3, the pH of the solution is in the range 3.0- 4.0, the impregnation is carried out from a twofold excess of the required volume of the impregnating solution, calculated taking into account the moisture capacity of the carrier. After that, the granules are dried in air for 24 hours at room temperature and calcined at 120 ° C for 8 hours.

After calcination at 550 ° C, the granules contain cobalt - 2 wt.%, Molybdenum –13 wt.%.

The catalyst in an amount of 10 g is loaded into a Berti reactor, the active component is sulfidized at 420 ° C with a solution of dimethyldisulfide in benzene with a 1.5-fold stoichiometric excess of sulfur relative to the amount of metals, and then they are tested in the hydrotreatment reactions of fuel oil at a temperature of 400 ° C, pressure 8 MPa The feed rate of M-100 fuel oil is 0.25 g of fuel oil / g-cat / h.

The test results are shown in the table.

Example 3

The preparation of the carrier is carried out by the method described in example 1, while porous zeolite-like silicoaluminophosphate up to 20 wt.% Is added to the paste. According to nitrogen and mercury porosimetry, the specific surface area of the obtained support was 120 m ² / g, specific pore volume 0.35 cm ³ / g, average micropore diameter 0.6 nm, mesopore 11 nm, macropores 90 nm, specific volume macropores make up 40% of the total specific pore volume, the external surface fraction is 70%.

The granules are impregnated with a solution of heteropoly compound Ni ₃ [PMo ₁₂ O ₄₀ ] ₂ and citric acid, for this a weighed portion of GPS is placed in an aqueous glycol solution with a ratio of Ni: Mo: glycol = 1: 6.5: 1.5, the pH of the solution is in the range of 3 , 0-4.0, the impregnation is carried out from a twofold excess of the required volume of the impregnating solution, calculated taking into account the moisture capacity of the carrier at a temperature of 80 ° C. After that, the granules are dried in air for 24 hours at room temperature and calcined at 120 ° C for 8 hours.

After calcination at 550 ° C, the granules contain nickel - 1 wt.%, Molybdenum - 6.5 wt.%.

The catalyst in an amount of 10 g is loaded into a Berti reactor, the active component is sulfidized at 420 ° C with a solution of dimethyldisulfide in benzene with a 1.5-fold stoichiometric excess of sulfur relative to the amount of metals, and then they are tested in the hydroprocessing of fuel oil at a temperature of 400 ° C, pressure 12 MPa The feed rate of M-100 fuel oil is 0.25 g of fuel oil / g-cat / h.

The test results are shown in the table.

Example 4

The preparation of the carrier is carried out by the method described in example 1.

The granules are impregnated with a solution of heteropoly compounds Co ₃ [PMo ₁₂ O ₄₀ ] ₂ , Ni ₃ [PMo ₁₂ O ₄₀ ] ₂ and glycol; for this, weighed portions of the reagents are placed in an aqueous glycol solution with the ratio Ni: Co: Mo: glycol = 1: 2: 12 : 3, the pH of the solution is in the range of 3.0-4.0, the impregnation is carried out by the moisture capacity of the carrier at a temperature of 40 ° C. After that, the granules are dried in air for 24 hours at room temperature and calcined at 120 ° C for 8 hours.

After calcination at 550 ° C, the granules contain nickel - 1 wt.%, Cobalt - 2 wt.%, Molybdenum - 20 wt.%.

The catalyst in an amount of 10 g is loaded into a Berti reactor, the active component is sulfidized at 420 ° C with a solution of dimethyl disulfide in benzene with a 1.5-fold stoichiometric excess of sulfur relative to the amount of metals, and then they are tested in the hydroprocessing of fuel oil at a temperature of 400 ° C, pressure 10 MPa The feed rate of M-100 fuel oil is 0.25 g of fuel oil / g-cat / h.

The test results are shown in the table.

Example 5

The preparation of the carrier is carried out by the method described in example 1, while the magnesium compound up to 5 wt.% Is added to the paste. According to nitrogen and mercury porosimetry, the specific surface of the carrier is 70 m ² / g, the specific pore volume is 0.15 cm ³ / g, the average diameter of the mesopores is 11 nm, the macropores are 90 nm, the specific volume of macropores is 40% of the total specific volume then, the proportion of the outer surface is 95%.

The granules are impregnated with a solution of heteropoly acid H ₃ [Co (OH) ₆ Mo ₆ O ₁₈ ] and EDTA; for this, weighed portions of the reagents are placed in an aqueous EDTA solution with the ratio Co: Mo: EDTA = 1: 6: 1.5, the pH of the solution is in the range 3.0-4.0, the impregnation is carried out from a twofold excess of the required volume of the impregnating solution, calculated taking into account the moisture capacity of the carrier at a temperature of 60 ° C. After that, the granules are dried in air for 24 hours at room temperature and calcined at 120 ° C for 8 hours.

After calcination at 550 ° C, the granules contain cobalt - 2 wt.%, Molybdenum - 20 wt.%.

The catalysts in an amount of 10 g are loaded into the Berti reactor, sulfide the active component at 420 ° C with a solution of dimethyldisulfide in benzene with a 1.5-fold stoichiometric excess of sulfur relative to the amount of metals, and then they are tested in the hydroprocessing reactions of fuel oil at a temperature of 550 ° C, pressure 10 MPa The feed rate of M-100 fuel oil is 0.25 g of fuel oil / g-cat / h.

The test results are shown in the table.

Example 6

The preparation of the carrier is carried out by the method described in example 1.

The granules are impregnated with a solution of heteropoly acid H ₂ [Ni (OH) ₆ Mo ₆ O ₁₈ ] and glycol; for this, weighed portions of the reagents are placed in an aqueous glycol solution with the ratio Ni: Mo: glycol = 1: 6: 2, the pH of the solution is in the range of 3, 0-5.0, the impregnation is carried out from a twofold excess of the required volume of the impregnating solution, calculated taking into account the moisture capacity of the carrier at room temperature. After that, the granules are dried in air for 24 hours at room temperature and calcined at 120 ° C for 8 hours.

After calcination at 550 ° C, the granules contain nickel - 1 wt.%, Molybdenum - 10 wt.%.

The catalyst in an amount of 10 g is loaded into a Berti reactor, the active component is sulfidized at 420 ° C with a solution of dimethyldisulfide in benzene with a 1.5-fold stoichiometric excess of sulfur relative to the amount of metals, and then they are tested in the hydroprocessing of fuel oil at a temperature of 420 ° C, pressure 15 MPa The feed rate of fuel oil M-100 is 0.5 g of fuel oil / g-cat / h.

The test results are shown in the table.

Example 7

Polymer microspheres in the form of a commercial product — acrylate dispersion — are used as a structure-forming template. Amorphous silica and AlOOH are used as a carrier precursor. Carrier samples are prepared by adding finely divided precursors to the powders of a dilute solution of nitric acid (10 ^-4 M) and a template solution with a mass template content of 30% in the paste. The paste is extruded to obtain granules with a diameter of 2.5 mm, a length of 5 mm The granules are dried in air for 24 hours and calcined in air at 600 ° C for 8 hours. According to nitrogen and mercury porosimetry, the specific surface of the aluminosilicate carrier is 120 m ² / g, the specific pore volume is 0.8 cm ³ / g, average the diameter of the mesopores is 12 nm, the macropores are 100 nm, the specific volume of macropores is 50% of the total specific pore volume, and the proportion of the outer surface is 60%.

The granules are impregnated with a solution of heteropoly acid H ₆ [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] and citric acid; for this, weighed portions of the reagents are placed in an aqueous glycol solution with the ratio Ni: Mo: citric acid = 1: 6: 1.2, the pH of the solution is in the range of 3.5-4.0, the impregnation is carried out according to the moisture capacity of the carrier at a temperature of 20 ° C. After that, the granules are dried in air for 24 hours at room temperature and calcined at 120 ° C for 8 hours.

After calcination at 550 ° C, the granules contain nickel - 2 wt.%, Molybdenum - 16 wt.%.

The catalyst in an amount of 10 g is loaded into a Berti reactor, the active component is sulfidized at 420 ° C with a solution of dimethyldisulfide in benzene with a 1.5-fold stoichiometric excess of sulfur relative to the sum of metals (Co + Mo), and then tested in the reaction of hydroprocessing of fuel oil at 420 ° C, pressure 15 MPa. The feed rate of M-100 fuel oil is 1 g of fuel oil / g-cat / h.

The test results are shown in the table.

Example 8

Polymer microspheres in the form of a commercial product — acrylate dispersion — are used as a structure-forming template. Alumino-silicate clay is used as a carrier precursor.

Carrier samples are prepared by adding a dilute nitric acid solution (10 ^-4 M) and a template solution with a template mass content of 30% to the aluminosilicate powder. The paste is extruded to obtain granules with a diameter of 2.5 mm, a length of 5 mm The granules are dried in air during the day and calcined in air at 600 ° C for 8 hours. According to nitrogen and mercury porosimetry, the specific surface of the aluminosilicate carrier is 150 m ² / g, the specific pore volume is 0.4 cm ³ / g, average the diameter of the mesopores is 10 nm, the macropores are 100 nm, the specific volume of macropores is 60% of the total specific pore volume, and the proportion of the outer surface is 60%.

The granules are impregnated with a solution of heteropoly acid H ₃ [Co (OH) ₆ W ₆ O ₁₈ ] and EDTA; for this, weighed portions of the reagents are placed in an aqueous glycol solution with the ratio Co: W: EDTA = 1: 6: 2, the pH of the solution is in the range of 3, 5-4.0, the impregnation is carried out from a twofold excess of the required volume of the impregnating solution, calculated taking into account the moisture capacity of the carrier at a temperature of 80 ° C. After that, the granules are dried in air for 24 hours at room temperature and calcined at 120 ° C for 8 hours.

After calcination at 550 ° C, the granules contain cobalt 1 wt.%, Tungsten - 18 wt.%.

The catalyst in an amount of 10 g is loaded into a Berti reactor, the active component is sulfidized at 420 ° C with a solution of dimethyldisulfide in benzene with a 1.5-fold stoichiometric excess of sulfur relative to the amount of metals, and then they are tested in the hydroprocessing of heavy Tatar oil (sulfur content of 3.50 wt.%, density at 20 ° C 934.2 kg / m ³ ) at a temperature of 450 ° C, a pressure of 12 MPa. The oil feed rate is 2 g-oil / g-cat / h.

The test results are shown in the table.

Example 9

The carrier is prepared by the method described in example 1, characterized in that NaY zeolite up to 15 wt.% Is added to the paste. According to nitrogen and mercury porosimetry, the specific surface of the carrier is 100 m ² / g, the specific pore volume is 0.8 cm ³ / g, the average diameter of the mesopores is 10 nm, the macropores are 100 nm, the specific volume of macropores is 40% of the total specific volume then, the proportion of the outer surface is 60%.

The granules are impregnated with an aqueous solution of heteropoly acid H ₃ [PMo ₆ W ₆ O ₄₀ ], the pH of the solution is in the range of 3.5-4.0, the impregnation is carried out from a twofold excess of the required volume of the impregnating solution, calculated taking into account the moisture capacity of the carrier at a temperature of 80 ° C. After that, the granules are dried in air for 24 hours at room temperature and calcined at 120 ° C for 8 hours.

After calcination at 550 ° C, the granules contain molybdenum - 8 wt.%, Tungsten - 16 wt.%.

The catalyst in an amount of 10 g is loaded into a Berti reactor, the active component is sulfidated at 420 ° C with a solution of dimethyldisulfide in benzene with a 1.5-fold stoichiometric excess of sulfur relative to the amount of metals, and then they are tested in the hydroprocessing of heavy Tatar oil (sulfur content of 3.50 wt.%, density at 20 ° C 934.2 kg / m ³ ) at a temperature of 400 ° C, a pressure of 10 MPa. The oil feed rate is 1 g-oil / g-cat / h.

The test results are shown in the table.

Example 10

The preparation of the carrier is carried out by the method described in example 1.

The granules are impregnated with a solution of heteropoly acid H ₄ [PVMo ₁₂ O ₄₀ ] and glycol, the pH of the solution is in the range of 3.0-4.0, the impregnation is carried out from a twofold excess of the required volume of the impregnating solution, calculated taking into account the moisture capacity of the carrier at a temperature of 80 ° C. After that, the granules are dried in air for 24 hours at room temperature and calcined at 120 ° C for 8 hours.

After calcination at 550 ° C, the granules contain vanadium - 0.8 wt.%, Molybdenum - 18 wt.%.

The catalyst in an amount of 10 g is loaded into a Berti reactor, sulfide is carried out sulfidation of the active component at 420 ° C with a solution of dimethyldisulfide in benzene with a 1.5-fold stoichiometric excess of sulfur relative to the amount of metals, and then they are tested in tar hydro-processing reactions (sulfur content 3.01 wt. %, density at 20 ° C 974.0 kg / m ³ ) at a temperature of 450 ° C, pressure 12 MPa. Tar feed rate is 0.5 g tar / g cat / h.

The test results are shown in the table.

Example 11

The preparation of the carrier is carried out by the method described in example 1.

The granules are impregnated with a solution of GPS Mo ₁₂ O ₃₀ (OH) ₁₀ H ₂ [Co (H ₂ O) ₃ ] ₄ and a solution of EDTA and citric acid, the pH of the solution is in the range of 3.0-5.0, the impregnation is carried out from a twofold excess of the required the volume of the impregnating solution, calculated taking into account the moisture capacity of the carrier at a temperature of 80 ° C. After that, the granules are dried in air for 24 hours at room temperature and calcined at 120 ° C for 8 hours.

After calcination at 550 ° C, the granules contain vanadium - 0.8 wt.%, Molybdenum - 18 wt.%.

The catalysts in an amount of 10 g are loaded into a Berti reactor, sulfide the active component at 420 ° C with a solution of dimethyldisulfide in benzene with a 1.5-fold stoichiometric excess of sulfur relative to the amount of metals, and then they are tested in tar hydroreactions at a temperature of 550 ° C, pressure 12 MPa Tar feed rate is 0.5 g tar / g cat / h.

The test results are shown in the table.

Table.

Change in the parameters of petroleum products relative to raw materials after hydroprocessing reactions

Example 1 2 3 4 5 6 7 8 9 10 eleven Sulfur conversion,% 20 25 thirty thirty fifty fifty 40 20 25 40 35 Density reduction, kg / m ³ 20 21 25 23 thirty thirty 27 20 21 25 25 Catalyst deactivation time,
h > 800

Claims (6)

1. The catalyst for the processing of heavy hydrocarbons, obtained by sulfidation of a composition containing an active component and a carrier, characterized in that the active component consists of a heteropoly compound containing at least one of the following compounds of the series [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , Co ₃ [PMo ₁₂ O ₄₀ ] ₂ , Ni ₃ [PMo ₁₂ O ₄₀ ] ₂ , [Co (OH) ₆ Mo ₆ O ₁₈ ] ^3- , [Ni (OH) ₆ Mo ₆ O ₁₈ ] ^2- , [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [Co (OH) ₆ W ₆ O ₁₈ ] ^3- , [PMo _n W _12-n O ₄₀ ] ^3- (where n = 1-11), [PV _n Mo _{12 -n} O ₄₀ ] ^{(3 + n) -} (where n = 1-4), Mo ₁₂ O ₃₀ (OH) ₁₀ H ₂ [Co (H ₂ O) ₃ ] ₄ or a mixture thereof and an organic additive such as lemon acid, glycol or EDTA, with the carrier represents alumina, silica, magnesium oxide, zeolite, aluminosilicate, porous aluminophosphate, porous silicoaluminophosphate and their combination, having a regular spatial structure of macropores, and the proportion of macropores with a size in the range from 50 nm to 15 μm is at least 30% in total specific pore volume, with a specific surface of at least 40 m ² / g with a fraction of the outer surface of at least 50% and a specific pore volume of at least 0.1 cm ³ / g, while the content of cobalt catalyst calcined at 550 ° C is not more than 20 wt.%, Nickel - not more than 2 0 wt.%, Molybdenum - not more than 20 wt.%, Tungsten - not more than 20 wt.%, The content of organic additives is 5-15 wt.% By weight of the catalyst. 2. A method of preparing a catalyst for the processing of heavy hydrocarbon feedstocks according to claim 1 by applying the active component to a carrier followed by heat treatment, characterized in that the carrier is impregnated with a solution of the precursor of the active component with an organic additive, such as citric acid, glycol or EDTA, by moisture capacity or from excess solution at a temperature of 20-80 ° C, dried in air at room temperature, calcined and then sulfidized. 3. The method according to p. 2, characterized in that the carrier is alumina, silica, magnesium oxide, zeolite, aluminosilicate, porous aluminophosphate, porous silicoaluminophosphate and their combination having a regular spatial structure of macropores, and the proportion of macropores with a size in the range from 50 nm to 15 μm is at least 30% of the total specific pore volume with a specific surface area of at least 40 m ² / g with an external surface fraction of at least 50% and a specific pore volume of at least 0.1 cm ³ / g. 4. A method of processing a heavy hydrocarbon feedstock in the presence of a catalyst, characterized in that the catalyst according to claim 1 or prepared according to any one of claims. 2, 3. 5. The method according to p. 4, characterized in that it is carried out at a temperature of 300-550 ° C, the feed rate through the catalyst of 0.1-2 g of feedstock / g of catalyst / h, in the presence of hydrogen supplied under pressure 7 -15 MPa. 6. The method according to p. 4, characterized in that as a heavy hydrocarbon feedstock use heavy oil or oil refining residues, such as fuel oil, tar.