RU2800374C1 - Method for processing heavy hydrocarbon raw materials - Google Patents

Abstract

FIELD: hydrocarbons.

SUBSTANCE: invention relates to a method for processing heavy hydrocarbon feedstock, including the successive passage of feedstock in the presence of hydrogen, supplied under pressure of 8-20 MPa, through a fixed catalyst bed 1 comprising aluminium oxide as a carrier, and calcium and/or magnesium compounds as an active component, having macropores with a regular spatial structure, through catalyst 2 comprising aluminium oxide as a carrier, and compounds of cobalt and/or nickel and/or molybdenum and/or tungsten as an active component, having macropores with a regular spatial structure, through catalyst 3 obtained by sulfiding a composition comprising an active ingredient and a carrier. 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), [PVnMo_12-nO₄₀]^(3+n)- (where n = 1-4), Mo₁₂O₃₀(OH)₁₀H₂[Co(H₂O)³]₄ or a mixture thereof and an organic additive, whereas the carrier is alumina, silicon oxide, zeolite, aluminosilicate, porous aluminophosphate, porous silicoaluminophosphate and their combination, having a regular spatial macropore structure. Further separation of gaseous products with the possibility of separating into separate oil products.

EFFECT: simultaneous involvement of raw materials in the processing without restrictions on viscosity and density, on the content of sulphur, metals and the production of oil products suitable for further processing to obtain commercial oil products without additional operations and the formation of non-recyclable residues.

10 cl, 3 tbl, 10 ex

Description

The invention relates to the field of processing of heavy hydrocarbon raw materials, including residual oil fractions using catalysts.

There is a need in the world for effective methods for processing low-quality hydrocarbon raw materials, for example, such as tar, fuel oil, high-viscosity oil, various oil residues - residues formed during oil refining, for example, in processes such as hydrocracking, catalytic cracking, delayed coking, pyrolysis, which make it possible to involve raw materials in the processing process without restrictions on viscosity and density, sulfur content, metals and at the same time obtain oil products, for example, such as diesel fraction, vacuum Gas oil (VGO) as a feedstock for secondary processes of hydrocracking (HA) and catalytic cracking (CC), residue after processing as a feedstock for coker units or a component of marine or boiler fuel, as well as when high-viscosity oil is used as a feedstock, is a synthetic oil suitable for processing according to known technologies, suitable for further processing to obtain commercial refined products, for example, such as diesel fuel, marine fuel, motor gasoline, petroleum coke.

There are various methods for processing heavy hydrocarbon raw materials using catalysts.

A known method of processing heavy oil feedstock on a protective layer of a bifunctional catalyst [RF Patent No. 2704123, published on 10/24/2019] containing aluminum oxide as a carrier, and calcium and/or magnesium and/or cobalt and/or nickel and/or molybdenum and/or tungsten compounds as an active component, the catalyst has macropores forming a regular spatial structure, in which heavy the oil feedstock is passed through a fixed catalyst bed at a temperature of 300-600°C, the feedstock feed rate through the catalyst is 0.2-2 g-feedstock/g-catalyst/h, in the presence of hydrogen supplied under a pressure of 8-12 MPa.

There is a known method for processing heavy oil feedstock on a protective layer of a catalyst [RF Patent No. 2704122, published on October 24, 2019], containing aluminum oxide as a carrier, and calcium and / or magnesium compounds as an active component, calcium not more than 10 wt.%, magnesium not more than 10 wt.%, the catalyst has macropores forming a regular spatial structure, in which heavy oil feedstock is passed through a fixed catalyst bed at a temperature of 3 00-600°C, feed rate through the catalyst 0.2-2 g-feedstock/g-catalyst/h, in the presence of hydrogen supplied at a pressure of 8-15 MPa.

A known method for processing heavy hydrocarbon raw materials [RF Patent No. 2717095, published on March 18, 2020] on a catalyst obtained by sulfiding a composition containing an active component from a heteropolycompound 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), [PVnMo_12-nO₄₀]^(3+n)-(where n = 1-4), Mo₁₂O_thirty(OH)₁₀H₂[Co(H₂O)³]₄ and an organic additive and a carrier, which is aluminum oxide, silicon oxide, magnesium oxide, zeolite, aluminosilicate, porous aluminophosphate, porous silicoaluminophosphate and their combination, having a regular spatial structure of macropores, which consists in passing the raw material through the fixed catalyst bed at a temperature of 300-550 ° C, the feed rate of the raw material through the catalyst is 0.1-2 g-feedstock/g-catalyst/h, in the presence of hydrogen, supplied under pressure of 7-15 MPa.

The listed methods make it possible to involve raw materials in the processing process without restrictive requirements for viscosity and density, sulfur content, metals, however, without additional operations and the formation of non-recyclable residues, they do not allow obtaining oil products suitable for further processing to obtain commercial oil products.

There is a known method for processing heavy oils by upgrading oil with subsequent distillation [Patent No. US10696910, published on 06/30/2020], including upgrading oil by bringing the raw material into contact with a hydrometallization catalyst, a transition catalyst, a hydronitrogenation catalyst and a hydrocracking catalyst, feeding oil into a separation device, while the final boiling point of heavy oil is 540°C.

A known method of processing atmospheric and vacuum precipitation [Residual hydrotreating catalysts [Electronic resource]: the official website of the company "Axens". Access mode: https://www.axens.net/solutions/catalysts-adsorbents-grading-supply/residue-hydrotreating-catalysts (data published online: 10/20/2021)] in a reactor system of series-connected reactors with a catalytic system characterized by three reaction zones, where the types and quantity of each catalyst are determined depending on the composition of the feedstock. The first reaction zone contains a catalyst for removing metals, deposits and salts, which catalyst can be selected from an alumina-cobalt, nickel-molybdenum catalyst or an alumina-nickel-molybdenum catalyst. The second reaction zone contains dual activity catalysts for metal removal and sulfur removal, which catalyst can be selected from alumina-cobalt, nickel-molybdenum or alumina-nickel-molybdenum catalyst. The third zone contains catalysts that provide deep sulfur removal, nitrogen removal and carbon recovery through hydrogenation, while the catalyst consists of aluminum oxide and cobalt, nickel. The disadvantage of this method is the limitation on the characteristics of the raw materials that can be involved in processing, namely, the method is aimed at processing atmospheric and vacuum residues.

This method is closest to the claimed and adopted as a prototype.

EFFECT: method for processing heavy hydrocarbon raw materials, which allows simultaneously involving raw materials in the processing process without restrictions on viscosity and density, sulfur content, metals, and obtaining oil products suitable for further processing to obtain commercial refined products without additional operations and the formation of unprocessable residues.

The technical result is achieved by the fact that the method of processing heavy hydrocarbon feedstock includes sequentially passing the feedstock in the presence of hydrogen, supplied under a pressure of 8-20 MPa, through a fixed layer of catalyst 1 containing aluminum oxide as a carrier, and as an active component of a calcium and/or magnesium compound having macropores with a regular spatial structure, through catalyst 2 containing aluminum oxide as a carrier, and as an active component - compounds of cobalt and/or nickel and/or molybdenum and/or tungsten, having macropores with a regular spatial structure, through catalyst 3 obtained by sulfiding a composition containing an active component and a carrier, while 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), [PVnMo_12-nO₄₀]^(3+n)-(where n = 1-4), Mo₁₂O_thirty(OH)₁₀H₂[Co(H_2O)³]₄ or a mixture of them and an organic additive, wherein the carrier is alumina, silicon oxide, zeolite, aluminosilicate, porous aluminophosphate, porous silicoaluminophosphate and their combination, having a regular spatial structure of macropores, and further separation of gaseous products with the possibility of separation into separate oil products.

The essence of the method lies in the fact that at the first stage, heavy hydrocarbon feedstock is passed through catalyst 1, which has macropores with a regular spatial structure, containing alkaline additives in the form of calcium and / or magnesium compounds, in the presence of hydrogen supplied under a pressure of 8-20 MPa, this makes it possible to involve various heavy oil feedstocks with high viscosity, density and a high content of sulfur and metals, for example, such as high-viscosity oil, tar, fuel oil, oil residues, which possible due to the presence of macropores with a regular spatial structure, and also allows you to minimize the metal content, viscosity, and partly the sulfur content in the reaction products.

Preferably, catalyst 1 contains an active component with a calcium content of not more than 10 wt.%, magnesium not more than 10 wt.%, has a specific surface area of at least 100 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, and the proportion of its macropores with a size in the range from 50 nm to 15 μm is at least 30% in the total specific pore volume of the catalyst.

Next, the raw material is passed through catalyst 2 containing aluminum oxide as a carrier, and cobalt and/or nickel and/or molybdenum and/or tungsten compounds as an active component, which has macropores with a regular spatial structure, which makes it possible to reduce the sulfur content as much as possible, remove the remaining metals, and also reduce the density of the raw material. The maximum sulfur reduction is achieved by the active components of the catalyst.

Preferably, in catalyst 2, the content of cobalt 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.%, the proportion of its macropores with a size in the range from 50 nm to 15 μm is not less than 30% in the total specific pore volume, and its specific surface is not less than 70 m ² /g with an external surface fraction of not less than 50% and a specific pore volume of at least 0.1 cm ³ /g.

In the next step, the feedstock is passed through catalyst 3 obtained by sulfiding a composition containing a heteropoly compound containing at least one of the following compounds [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), [PVnMo_12-nO₄₀]^(3+n)-(where n = 1-4), Mo₁₂O_thirty(OH)₁₀H₂[Co(H₂O)³]₄ or a mixture of them and an organic additive, while the carrier is aluminum oxide, silicon oxide, zeolite, aluminosilicate, porous aluminophosphate, porous silicoaluminophosphate and their combination, which has a regular spatial structure of macropores, which makes it possible to further purify the raw material from sulfur, reduce viscosity and density, and carry out a hydrocracking reaction to obtain oil products with a lower boiling point.

Preferably, catalyst 3 contains citric acid, glycol or EDTA as an organic additive, the proportion of its macropores with a size in the range from 50 nm to 15 μm is at least 30% in the total specific pore volume, the specific surface area is at least 40 m ² /g, the proportion of the external surface is at least 50% and the specific pore volume is at least 0.1 cm ³ /g, while the content of cobalt in the catalyst calcined at 550°C is not more than 20 wt.%, nickel - no more than 20 wt.%, molybdenum - no more than 20 wt.%, tungsten - no more than 20 wt.%, the content of the organic additive is 5-15 wt.% of the weight of the catalyst.

Preferably, the raw material is passed through the catalysts at a volumetric feed rate of raw materials through the catalysts of 0.15 - 1 h ^-1 and at a temperature of 340-500°C. During the course of chemical reactions, the temperature can fluctuate up to 60 ° C in the given parameters.

After passing the feedstock through 3 catalysts, gaseous products and naphtha are separated, which makes it possible to obtain marine fuel that meets MARPOL requirements. If it is necessary to obtain other marketable products of oil refining after separation of gaseous products, the feedstock can be divided into various petroleum products, for example, such as diesel fraction, vacuum gas oil (VGO) as a feedstock for secondary processes of hydrocracking (HA) and catalytic cracking (CC), the residue after processing, as a feedstock for coker units or a component of marine or boiler fuel, as well as when using high-viscosity oil as a feedstock - synthetic oil suitable for processing according to known technologies, which can be processed according to known technologies m with the receipt of marketable products of oil refining. In this case, unrecyclable residues are not formed.

The set of features of the proposed method for processing heavy hydrocarbon raw materials makes it possible to simultaneously involve raw materials in the processing process without restrictions on viscosity and density, on the content of sulfur, metals, to efficiently process raw materials, while removing sulfur, metals, and also to obtain various oil products to obtain marketable refined products.

The method of processing heavy hydrocarbon raw materials in general is carried out as follows.

In the course of the experiments, 10 g of catalyst 1 containing aluminum oxide as a carrier is poured into one reactor, and 20 g of catalyst 2 is poured into another reactor, containing aluminum oxide as a carrier, and cobalt and/or nickel and/or molybdenum and/or tungsten compounds having macropores with a regular spatial structure as an active component, in the third reactor is filled with 20 g of catalyst 3 obtained by sulfiding a composition containing a heteropoly compound as an active component, containing compounds from 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), [PVnMo_12-nO₄₀]^(3+n)-(where n = 1-4), Mo₁₂O_thirty(OH)₁₀H₂[Co(H₂O)³]₄ and an organic additive, and as a carrier - aluminum oxide, silicon oxide, zeolite, aluminosilicate, porous aluminophosphate, porous silicoaluminophosphate and their combination, which has a regular spatial structure of macropores.

The feedstock is sequentially passed in the presence of pressurized hydrogen through 3 catalysts at a given temperature and feed space velocity, after which gaseous products are separated and, if necessary, separated into oil products.

Example 1

Tar 1 is used as a raw material, the characteristics of the raw material are presented in Table 1. The raw material is sequentially passed through 3 catalysts (catalyst 1 - sample 1, catalyst 2 - sample 1, catalyst 3 - sample 2) at a temperature of 450°C, in the presence of hydrogen supplied under a pressure of 14 MPa and a feed space velocity (SFS) of 0.5 h ^-1 , then the gaseous product is separated and MARPOL RMG 1380 marine fuel is obtained Marine fuel characteristics are presented in Table 3, catalyst characteristics are presented in Table 2.

After passing the raw material through each catalyst, the raw material is analyzed. The characteristics of the feedstock after each reactor are shown in Table 3.

Example 2

Tar 2 is used as a raw material, the characteristics of the raw material are presented in Table 1. The raw material is sequentially passed through 3 catalysts (catalyst 1 - sample 1, catalyst 2 - sample 1, catalyst 3 - sample 2) at a temperature of 380 ° C, in the presence of hydrogen supplied under a pressure of 16 MPa and 0.25 h ^-1 SPPS, then the gaseous product is separated and MARPOL RMG 380 marine fuel is obtained. Marine fuel characteristics are presented in table 3, the characteristics of the catalysts are presented in table 2.

After passing through each catalyst, the raw material is analyzed. The characteristics of the feedstock after each reactor are shown in Table 3.

Example 3

Fuel oil 1 is used as a raw material, the characteristics of the raw material are presented in Table 1. The raw material is sequentially passed through 3 catalysts (catalyst 1 - sample 3, catalyst 2 - sample 2, catalyst 3 - sample 1) at a temperature of 420 °C, in the presence of hydrogen supplied under a pressure of 8 MPa and 0.5 h ^-1 OSPS, then the gaseous product is separated and the diesel fraction, VGO and the residue after processing are obtained. Characteristics of petroleum products are presented in table 3, characteristics of catalysts are presented in table 2.

After passing through each catalyst, the raw material is analyzed. The characteristics of the feedstock after each reactor are shown in Table 3.

Example 4

Fuel oil 2 is used as a raw material, the characteristics of the raw material are presented in Table 1. The raw material is sequentially passed through 3 catalysts (catalyst 1 - sample 3, catalyst 2 - sample 2, catalyst 3 - sample 1) at a temperature of 450 °C, in the presence of hydrogen supplied under a pressure of 20 MPa and SPPS 1 h ^-1 , then the gaseous product, diesel fraction, VGO and the residue after processing are separated. Characteristics of petroleum products are presented in table 3, characteristics of catalysts are presented in table 2.

After passing through each catalyst, the raw material is analyzed. The characteristics of the feedstock after each reactor are shown in Table 3.

Example 5

Fuel oil 2 is used as a raw material, the characteristics of the raw material are presented in Table 1. The raw material is sequentially passed through 3 catalysts (catalyst 1 - sample 3, catalyst 2 - sample 2, catalyst 3 - sample 1) at a temperature of 410 °C, in the presence of hydrogen supplied under a pressure of 16 MPa and OSSP 0.15 h ^-1 , then the gaseous product is separated and the diesel fraction, VGO and the residue after processing are obtained. Characteristics of petroleum products are presented in table 3, characteristics of catalysts are presented in table 2.

After passing through each catalyst, the raw material is analyzed. The characteristics of the feedstock after each reactor are shown in Table 3.

Example 6

The oil residue is used as a feedstock, the characteristics of the feedstock are presented in Table 1. The feedstock is sequentially passed through 3 catalysts (catalyst 1 - sample 2, catalyst 2 - sample 3, catalyst 3 - sample 3) at a temperature of 38 °C, in the presence of hydrogen supplied under a pressure of 12 MPa and 0.5 h ^-1 SPPS, then the gaseous product is separated and the feedstock is separated into VGO and the residue after processing. The characteristics of the obtained oil products are presented in table 3, the characteristics of the catalysts are presented in table 2.

After passing through each catalyst, the raw material is analyzed. The characteristics of the feedstock after each reactor are shown in Table 3.

Example 7

High-viscosity oil is used as a feedstock, the characteristics of the feedstock are presented in Table 1. The feedstock is sequentially passed through 3 (catalyst 1 - sample 2, catalyst 2 - sample 3, catalyst 3 - sample 3) catalyst at a temperature of 400 °C, in the presence of hydrogen supplied under a pressure of 10 MPa and 0.8 h ^-1 SPPS, then the gaseous product is separated and a synthetic product is obtained. The characteristics of the oil are presented in table 3, the characteristics of the catalysts are presented in table 2.

After passing through each catalyst, the raw material is analyzed. The characteristics of the feedstock after each reactor are shown in Table 3.

Example 8

Tar 1 is used as a raw material, the characteristics of the raw material are presented in Table 1. The raw material is sequentially passed through 3 catalysts (catalyst 1 - sample 1, catalyst 2 - sample 1, catalyst 3 - sample 1) at a temperature of 340 ° C, in the presence of hydrogen supplied under a pressure of 20 MPa and 0.2 h ^-1 SPPS, then the gaseous product is separated and the residue after processing and VGO is obtained. Characteristics of petroleum products are presented in table 3, characteristics of catalysts are presented in table 2.

After passing through each catalyst, the raw material is analyzed. The characteristics of the feedstock after each reactor are shown in Table 3.

Example 9

The oil residue is used as a feedstock, the characteristics of the feedstock are presented in Table 1. The feedstock is successively passed through 3 catalysts (catalyst 1 - sample 2, catalyst 2 - sample 3, catalyst 3 - sample 3) at a temperature of 500 °C, in the presence of hydrogen supplied under a pressure of 12 MPa and 0.3 h ^-1 ISPS, then the gaseous product is separated and the feedstock is separated into VGO and the residue after processing. The characteristics of the obtained oil products are presented in table 3, the characteristics of the catalysts are presented in table 2.

After passing through each catalyst, the raw material is analyzed. The characteristics of the feedstock after each reactor are shown in Table 3.

Example 10

Tar 2 is used as a raw material, the characteristics of the raw material are presented in Table 1. The raw material is sequentially passed through 3 catalysts (catalyst 1 - sample 1, catalyst 2 - sample 1, catalyst 3 - sample 1) at a temperature of 420 °C, in the presence of hydrogen supplied under a pressure of 16 MPa and 0.5 h ^-1 OHPS, then the gaseous product is separated and the raw material is separated into VGO and the residue after processing. The characteristics of the obtained oil products are presented in table 3, the characteristics of the catalysts are presented in table 2.

After passing through each catalyst, the raw material is analyzed. The characteristics of the feedstock after each reactor are shown in Table 3.

Table 1 - Types and characteristics of heavy hydrocarbon feedstock

Type of raw material Characteristics Density at 15С, kg/m ³ Kinematic viscosity at 100C, cSt. Sulfur content, % wt. Metal content (vanadium + nickel), ppm Tar 1 985 300 3.01 175 Tar 2 1030.3 247 2.78 333 Fuel oil 1 958 35 2.53 122 Fuel oil 2 961 42 2.30 151 Oil residue 1001.1 253 3.5 215 High viscosity oil 1 950.0 38 5.75 86

Table 2 - Composition of catalysts

Catalyst Sample Composition, content, % wt. Share of macropores, % Specific surface, m ² /g Catalyst 1 1 Al ₂ O _3, Mg - 3.3 35 111 2 Al ₂ O ₃ , Ca - 4.5 43 168 3 Al ₂ O ₃ , Mg - 3.8, Ca - 4.2 38 144 Catalyst 2 1 Al ₂ O _3, Ni - 7.4, Mo - 16.7 55 72 2 Al ₂ O _3, Ni - 0.6, Mo - 15.9, W - 4.2 38 77 3 _{Al2O3 _}
Ni - 1.2, Mo - 7.9, Co - 4.5 49 79 Catalyst 3 1 Al ₂ O _3, Ni - 6, Mo - 13.4, aluminophosphate - 5.1, aluminosilicate - 4.3 74 84 2 Al ₂ O _3, W - 3.6, Ni - 0.6, Mo - 8.6, zeolite - 13 68 124 3 Al ₂ O _3, Ni - 2.5, Mo - 14.2, V - 0.06, silicoaluminophosphate - 13 70 94

Table 3 - Process parameters

Example Raw material Parameters (temperature, pressure, ISPS) Data after 1 reactor: density at 15°C, kg/m3, viscosity at 100°C, cSt, sulfur, wt %, metals, ppm Data after 2 reactors: density at 15°C, kg/m3, viscosity at 100°C, cSt, sulfur, wt %, metals, ppm Data after 3 reactors: Density at 15°C, kg/m3, Viscosity at 100°C, cSt, Sulfur, wt %, Metals, ppm Type and characteristics of obtained oil products 1 Tar 1 T- 450°С,
R-14 MPa, OSPS- 0.5 h ^-1 Density - 962
Viscosity - 73
Sulfur -2.3,
Metals - 78 Density - 943
Viscosity - 21
Sulfur - 0.8
Metals - 31 Density - 939
Viscosity - 19
Sulfur - 0.49
Metals 17 Marine fuel MARPOL brand RMG 380:
sulfur -0.49% of the mass,
viscosity at 50°C -186 cSt, density at 15°C -939 2 Tar 2 T- 380°С,
R-16MPa, OSPS- 0.25 h ^-1 Density - 987
Viscosity - 61
Sulfur -2.2
Metals - 54 Density - 940
Viscosity - 31
Sulfur - 0.8
Metals - 28 Density - 924
Viscosity - 11
Sulfur - 0.44
Metals - 15 Marine fuel MARPOL brand RMG 380:
sulfur -0.44% mass, viscosity at 50°С -176 cSt, density at 15°С -924 3 Fuel oil 1 T- 420°С,
R-8 MPa, OSPS- 0.5 h ^-1 Density - 921
Viscosity - 11
Sulfur -1.9
Metals - 86 Density - 895
Viscosity - 5
Sulfur - 0.5
Metals - 36 Density - 875
Viscosity - 4
Sulfur - 0.09
Metals - 6 Diesel fraction:
sulfur - 0.01% mass, viscosity at 50°С -3.0 cSt, density at 15°С - 844
VGO:
sulfur - 0.06% mass,
Residue after processing:
sulfur - 0.4% 4 Fuel oil 2 T- 450°С,
R-20 MPa, OSPS- 1 h ^-1 Density - 926
Viscosity - 17
Sulfur -1.84
Metals - 91 Density - 902
Viscosity - 9
Sulfur - 0.85
Metals - 42 Density - 884
Viscosity - 5
Sulfur - 0.2
Metals - 14 Diesel fraction:
sulfur - 0.1% mass, viscosity at 50°С -3.0 cSt, density at 15°С - 839
VGO:
sulfur - 0.3% mass
Residue after processing:
sulfur - 0.9% 5 Fuel oil 2 T- 410°С,
R-16 MPa, OSPS- 0.15 h ^-1 Density - 919
Viscosity - 14
Sulfur -1.7
Metals - 75 Density - 894
Viscosity - 8
Sulfur - 0.65
Metals - 34 Density - 878
Viscosity - 4
Sulfur - 0.09
Metals - 7 Diesel fraction:
sulfur - 0.02% mass, viscosity at 50°С -2.0 cSt, density at 15°С - 835
VGO:
sulfur - 0.1% mass, Residue after processing:
sulfur - 0.35% wt. 6 Oil residue T- 380°С,
R-12 MPa, OSPS- 0.5 h ^-1 Density - 989
Viscosity - 90
Sulfur -3.1
Metals - 71 Density - 978
Viscosity - 39
Sulfur - 2.0
Metals - 48 Density - 967
Viscosity - 30
Sulfur - 1.6
Metals - 35 VGO:
sulfur -1.0%, \ mass, Residue after processing:
sulfur -2.3% wt. 7 High viscosity oil T- 400°С,
R-10 MPa, OSPS- 0.8 h ^-1 Density - 920
Viscosity - 15
Sulfur -4.3
Metals - 34 Density - 901
Viscosity - 6
Sulfur - 2.8
Metals - 15 Density - 884
Viscosity - 4
Sulfur - 1.7
Metals - 6 Synthetic oil:
sulfur -1.7% mass, viscosity at 50°С -15 cSt, density at 15°С -884 8 Tar 1 T- 340°С,
R-20 MPa, OSPS- 0.2 h ^-1 Density - 972
Viscosity - 92
Sulfur -2.4
Metals - 84 Density - 953
Viscosity - 36
Sulfur - 1.2
Metals - 42 Density - 946
Viscosity - 22
Sulfur - 0.7
Metals - 25 VGO:
sulfur - 0.2% mass,
Residue after processing:
sulfur - 0.8% 9 Remainder 1 T- 500°С,
R-12 MPa, OSPS- 0.3 h ^-1 Density - 982
Viscosity - 42
Sulfur -2.9
Metals - 67 Density - 955
Viscosity - 28
Sulfur - 1.8
Metals - 41 Density - 938
Viscosity - 19
Sulfur - 0.7
Metals - 28 VGO:
sulfur - 0.2% wt.,
Residue after processing:
sulfur - 1.1% 10 Tar 2 T- 420°С,
R-16 MPa, OSPS- 0.5 h ^-1 Density - 993
Viscosity - 77
Sulfur -2.4
Metals - 72 Density - 966
Viscosity - 56
Sulfur - 1.4
Metals - 38 Density - 951
Viscosity - 35
Sulfur - 0.9
Metals - 29 VGO:
sulfur - 0.25% wt.,
Residue after processing:
sulfur - 1.1%

Claims (15)

1. A method for processing heavy hydrocarbon raw materials, including - successive passage of raw materials in the presence of hydrogen supplied under a pressure of 8-20 MPa, - through a fixed bed of catalyst 1 containing aluminum oxide as a carrier, and as an active component of a calcium and / or magnesium compound having macropores with a regular spatial structure, - through catalyst 2 containing aluminum oxide as a carrier, and cobalt and/or nickel and/or molybdenum and/or tungsten compounds as an active component, having macropores with a regular spatial structure, - through catalyst 3 obtained by sulfiding a composition containing an active component and a carrier, while 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), [PVnMo_12-nO₄₀]^(3+n)-(where n = 1-4), Mo₁₂O_thirty(OH)₁₀H₂[Co(H₂O)₃]₄ or a mixture of them and an organic additive, while the carrier is alumina, silicon oxide, zeolite, aluminosilicate, porous aluminophosphate, porous silicoaluminophosphate and their combination, having a regular spatial structure of macropores, - and further separation of gaseous products with the possibility of separation into separate oil products. 2. The method according to p. 1, characterized in that the catalyst 1 contains an active component with a calcium content of not more than 10 wt.%, magnesium is not more than 10 wt.%. 3. The method according to p. 1, characterized in that the proportion of macropores of catalyst 1 with a size in the range from 50 nm to 15 μm is at least 30% in the total specific pore volume of catalyst 1. 4. The method according to p. 1, characterized in that the catalyst 1 has a specific surface area of at least 100 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. 5. The method according to p. 1, characterized in that in the catalyst 2 the content of cobalt is not more than 20 wt.%, nickel - not more than 20 wt.%, molybdenum - not more than 20 wt.%, tungsten - not more than 20 wt.%. 6. The method according to p. 1, characterized in that in the catalyst 2 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. 7. The method according to claim 1, characterized in that the catalyst 2 has a specific surface area of at least 70 m ² /g with an external surface ratio of at least 50% and a specific pore volume of at least 0.1 cm ³ /g. 8. The method according to p. 1, characterized in that the catalyst 3 contains citric acid, glycol or EDTA as an organic additive. 9. The method according to claim 1, characterized in that the proportion of macropores with a size in the range from 50 nm to 15 μm in catalyst 3 is at least 30% in 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, while the content of cobalt in catalyst 3 calcined at 550 ° C is not more than 20 wt.%, nickel - no more than 20 wt.%, molybdenum - no more than 20 wt.%, tungsten - no more than 20 wt.%, the content of the organic additive is 5-15 wt.% of the weight of the catalyst. 10. The method according to p. 1, characterized in that the raw material is passed through the catalysts at a volumetric feed rate of the raw material through the catalysts 0.15 - 1 h ^-1 and at a temperature of 340-500°C.