A hydrogenation method for preparing diesel fractions from oil-based raw materials

Abstract

The present invention relates to a hydrogenation method for preparing diesel fractions from oil-based raw materials, which includes: the oil-based raw materials are contacted with a hydroconversion catalyst in the presence of hydrogen to mainly carry out hydrodeoxygenation and hydroisomerization reactions. After the reaction effluent is subjected to gas-liquid separation, the obtained liquid-phase stream is fractionated to obtain a diesel fraction, and the content of isoparaffins in the diesel fraction is at least 40% by weight. The present invention can obtain a diesel fraction with a low freezing point by treating oil-based raw materials in one step. Compared with the prior art, the process flow is simplified, and the catalyst has high stability and low cost.

Description

Technical Field

[0001] The present invention relates to the technical field of oil raw material treatment, and particularly relates to a hydrogenation method for preparing diesel fractions from oil raw materials. Background Art

[0002] With the tightening of the supply of traditional fossil energy and the increasing pressure of carbon dioxide emission reduction, how to effectively reduce the carbon dioxide gas emissions while increasing the fuel supply is an important issue faced by the refining industry. Developing biofuels is considered to be one of the effective means to solve this problem. The production of jet fuel using oil as a raw material usually adopts a two-step hydrogenation process. First, the oil raw material is hydrogenated to obtain hydrocarbon compounds; then the hydrocarbon compounds are hydrogenated and converted to prepare jet fuel components meeting the jet fuel standards.

[0003] Biofuels have gradually attracted people's attention mainly for the following reasons: 1. Biofuels are renewable energy sources; 2. The carbon-containing characteristics of biofuels are close to those of existing fuels; 3. The carbon dioxide absorbed by the precursors of biofuels can reduce the net emissions of greenhouse gases; 4. Bioenergy is more evenly distributed than fossil energy.

[0004] The traditional method for converting vegetable oil or other fatty acid derivatives into liquid fuels is transesterification. The transesterification method is an ester exchange reaction using alcohol under the action of a catalyst to convert the triglycerides forming vegetable oil into corresponding fatty acid alkyl esters, usually fatty acid methyl esters. However, the low-temperature fluidity of fatty acid methyl esters limits their use in low-temperature environments. The low-temperature fluidity of fatty acid methyl esters is determined by the chain characteristics of their fatty acids. The presence of carbon-carbon double bonds can improve the low-temperature fluidity but reduces the stability of fatty acid methyl esters. In addition, the presence of oxygen in fatty acid methyl esters will result in higher NOx emissions compared to traditional diesel fuels.

[0005] Diesel components with high cetane numbers can be produced from oils through hydrogenation technology. For example, US4992605A discloses a method for producing high-cetane hydrocarbons, and the product is mainly n-alkanes with C15-C18, having a relatively high freezing point and poor low-temperature fluidity. US5705722A discloses a method for preparing liquid hydrocarbons within the diesel boiling range from a biomass raw material containing beef tallow with a relatively high content of unsaturated compounds. The raw material is hydrogenated at a temperature of at least 350 °C. Similarly, the product obtained by this method is n-alkanes with a relatively high freezing point and poor low-temperature fluidity.

[0006] To improve the low-temperature flow properties of hydrogenated products, the usual method is to carry out isomerization reaction on the products. For example, EP1396531 discloses a method for converting a raw material selected from vegetable oil, animal oil or fish oil into liquid hydrocarbons, the method comprising a hydrodeoxygenation step followed by a hydroisomerization step. The isomerization step operates on the countercurrent principle to remove impurities such as hydrogen sulfide and water generated in the hydrodeoxygenation step, avoiding poisoning of the noble metal isomerization catalyst.

[0007] CN101583694B discloses a method for preparing a hydrocarbon fraction that can be used as diesel fuel or a diesel fuel component. The method first hydrodeoxygenates a biological raw material containing fatty acid esters that may contain a certain amount of free fatty acids, and then includes a purification step and a washing step for separating the liquid fraction from the hydrodeoxygenation step, and a hydroisomerization step. In order to overcome the need for purification of the liquid hydrocarbons produced in the hydrodeoxygenation process when using an isomerization catalyst of noble metal or reduced metal.

[0008] US2006 / 0207166 discloses a method for producing diesel fuel from animal and vegetable oils and fats. The method uses a catalyst with platinum and palladium supported on an acidic carrier in a reactor to achieve hydrodeoxygenation and isomerization reactions, and the resulting product is alkanes with C14 - C18, where the ratio of isoparaffins to normal paraffins is 2 - 8.

[0009] CN103289824A discloses a conversion process of oils and fats. The method converts oils and fats into hydrocarbon compounds through a one-step catalytic reaction. The yield of converting oils and fats into C11 - C24 alkanes is greater than 70 wt%, and the selectivity of isoparaffins is greater than 60 wt%. The catalyst used is a metal supported on an acidic carrier, and the acidic carrier includes zeolite and / or heteroatom-substituted aluminophosphate molecular sieve (AIPO-n), preferably SAPO (silicoaluminophosphate molecular sieve) or MeAPO (metal aluminophosphate molecular sieve).

[0010] CN103920528A discloses a catalyst for the one-step hydrodeoxygenation cracking isomerization of oils and fats to prepare aviation kerosene components and its preparation method. The catalyst is a noble metal supported on a composite solid acid carrier, and its composition is 0.2% - 0.5% of Pd, 5% - 85% of beta molecular sieve, and 10% - 94.8% of alumina.

[0011] From the above prior art of the one-step method, the active component of its catalyst is a reduced metal. Compared with the sulfided catalyst, the reduced catalyst is prone to deactivation, especially for noble metal catalysts, there will be problems of poor catalyst stability.

[0012] In view of the existing technology, when preparing diesel fractions from oil and fat raw materials, in order to reduce the low-temperature fluidity of diesel, a two-stage hydrogenation process is usually adopted. First, hydrodeoxygenation is carried out to obtain a fraction mainly composed of n-alkanes, and then hydroisomerization reaction is carried out to lower the freezing point of the product and improve its low-temperature fluidity. When a one-step hydrogenation process is adopted, the catalyst has the disadvantage of poor stability. Summary of the Invention

[0013] The present invention is to solve the technical problems of poor catalyst stability and high catalyst cost existing in the one-step production of diesel fractions from oil and fat raw materials in the prior art.

[0014] The present invention provides a hydrogenation method for preparing diesel fractions from oil and fat raw materials, including: the oil and fat raw materials are contacted with a hydroconversion catalyst in the presence of hydrogen to mainly carry out hydrodeoxygenation and hydroisomerization reactions. After the reaction effluent is subjected to gas-liquid separation, the obtained liquid-phase stream is fractionated to obtain a diesel component, and the content of isoparaffins in the diesel fraction is at least 40% by weight;

[0015] The hydroconversion catalyst contains a carrier and a hydrogenation active metal component. The carrier contains alumina and silica-alumina. Based on the carrier, the content of the alumina is 20-80% by weight, and the content of the silica-alumina is 80-20% by weight. The alumina is an alumina in which the pore volume of pores with a pore diameter less than 60 Å accounts for more than 25% of the total pore volume; the hydrogenation active metal component is at least one selected from Group VIB metal elements and at least one selected from Group VIII metal elements. The Group VIB metal element is molybdenum and / or tungsten, and the Group VIII metal element is cobalt and / or nickel; based on oxides and based on the hydroconversion catalyst, the content of cobalt and / or nickel is 1-10% by weight, and the content of molybdenum and / or tungsten is 5-40% by weight.

[0016] In the present invention, the oil and fat raw materials include one or more of various animal and vegetable oils and fats and waste cooking oil.

[0017] The animal and vegetable oils and fats include vegetable oils and animal fats, as well as raw materials containing glycerides and free fatty acids, and fatty acid methyl esters or fatty acid ethyl esters prepared by transesterification of vegetable oils and / or animal fats. The glycerides include triglycerides, diglycerides and monoglycerides. The vegetable oils include, but are not limited to, one or more of soybean oil, rapeseed oil, cottonseed oil, corn oil, rice bran oil, sunflower oil, peanut oil, castor oil, sesame oil, Chinese prickly ash seed oil, tea oil, coconut oil, olive oil, Pistacia chinensis oil, palm oil, tung oil, Jatropha curcas oil, pine resin oil, and Sapium sebiferum oil.

[0018] The described catering waste oil is the oil waste that is not suitable for further consumption generated in the processing of animal and vegetable oils and edible consumption. It includes fatty acids, acidified oil, etc. generated during the production of edible oil from oilseeds; various catering waste oils such as frying waste oil, kitchen waste oil, swill oil, etc. generated from the use of edible oil by households, hotels, the catering industry, and food production enterprises; animal fats by-produced in meat production and processing, and also edible oil that has exceeded its shelf life, etc.

[0019] In the present invention, the oil raw materials are contacted with a hydroconversion catalyst in the presence of hydrogen, and reactions including olefin saturation, hydrodeoxygenation, hydrodecarboxylation, hydrodecarbonylation, hydrodesulfurization, hydrodenitrogenation, isomerization of normal paraffins, and a small amount of cracking occur. The reaction products are alkanes with carbon numbers from 3 to 24, and also by-products such as water, carbon monoxide, carbon dioxide, and hydrogen sulfide. The reaction effluent is separated to obtain a liquid hydrocarbon product by methods of gas-liquid separation and fractionation. The separated gas product can be separated to obtain hydrogen as recycle hydrogen through hydrogen purification technology. Optional hydrogen purification technologies can include traditional hydrogen purification technologies such as pressure swing adsorption PSA and membrane separation.

[0020] When producing diesel fractions from oil as the raw material, the low-temperature fluidity of diesel is related to the content of normal paraffins. The higher the content of normal paraffins, the higher the freezing point of diesel. After isomerizing normal paraffins into isoparaffins, its freezing point can be reduced. The inventors of the present invention have found through in-depth research that when the content of isoparaffins in the diesel fraction is higher than 40% by weight, the freezing point of diesel can be reduced to below 0°C; however, when the content of isoparaffins is further increased, while the freezing point of diesel is reduced, its cetane number will also decrease. And, with the increase in the degree of isomerization, more cracking side reactions will occur, resulting in a reduction in the yield of the diesel fraction. Therefore, in the method provided by the present invention, the content of isoparaffins in the obtained diesel fraction is controlled to be at least 40% by weight. The obtained diesel fraction can be used alone or as a blending component and mixed with fossil-based diesel.

[0021] In one embodiment of the present invention, the initial boiling point of the diesel fraction is 170 - 205°C, and the final boiling point is 290 - 350°C.

[0022] In one embodiment of the present invention, the reaction conditions for hydroconversion: reaction temperature 250 - 450°C, pressure 3.0 - 10.0 MPa, liquid hourly space velocity 0.1 - 10 h -1 , and the hydrogen-oil volume ratio is 300 - 2000 Nm 3 / m 3 . In the preferred case, the reaction conditions for hydroconversion: reaction temperature 300 - 400°C, pressure 4.0 - 8.0 MPa, liquid hourly space velocity 0.5 - 5 h -1 , and the hydrogen-oil volume ratio is 500 - 1500 Nm 3 / m 3。

[0023] In one embodiment of the present invention, the hydroconversion catalyst contains a support and a hydrogenation active metal component. The support contains alumina and silica-alumina. Based on the support, the content of the alumina is 25-75% by weight, and the content of the silica-alumina is 75-25% by weight.

[0024] In one embodiment of the present invention, the alumina is an alumina in which the pore volume of pores with a pore diameter less than 60 Å accounts for more than 30% of the total pore volume.

[0025] The alumina is selected from one or more transition phase aluminas among γ, η, θ, δ, and χ, or may be one or more transition phase aluminas among γ, η, θ, δ, and χ containing one or several doping components selected from titanium, magnesium, boron, zirconium, thorium, niobium, and rare earths. Preferably, it is γ-alumina and / or γ-alumina containing one or several doping components selected from titanium, magnesium, boron, zirconium, thorium, niobium, and rare earths. The alumina described above can be a commercially available product or can be prepared by any existing technology.

[0026] In one embodiment of the present invention, the silica-alumina is a silica-alumina having a characteristic X-ray diffraction pattern of γ-alumina. Based on the silica-alumina, the silica-alumina contains 5-60% by weight of silica and 40-95% by weight of alumina. In a preferred case, based on the silica-alumina, the silica-alumina contains 10-45% by weight of silica and 55-90% by weight of alumina.

[0027] The silica-alumina described above can be a commercially available product or can be prepared by any existing technology.

[0028] In one embodiment of the present invention, the preparation of the support includes mixing, shaping, and calcining silica-alumina and / or its precursor with alumina and / or the precursor of alumina, where the amounts of each component are such that the final support is obtained. The precursor of alumina is selected from hydrated alumina, preferably boehmite among them; the precursor of the silica-alumina preferably has a boehmite structure. They can be commercially available products or can be prepared by any existing technology. After calcination, the alumina precursor is an alumina in which the pore volume of pores with a pore diameter less than 60 Å accounts for more than 25%, preferably more than 30%, and further preferably more than 35% of the total pore volume.

[0029] The calcination is carried out by the methods and conditions customary in the art. For example, the calcination temperature can be 350-650 °C; preferably 400-600 °C, and the calcination time is 2-6 hours, preferably 3-5 hours.

[0030] In one embodiment of the present invention, based on the hydrogenation conversion catalyst and calculated as oxides, the content of cobalt and / or nickel is 2-8% by weight, and the content of molybdenum and / or tungsten is 10-35% by weight.

[0031] In one embodiment of the present invention, the method for introducing the hydrogenation active metal component is to contact the carrier with a solution of a metal compound containing the hydrogenation active metal component under conditions sufficient to deposit an effective amount of the metal component on the carrier, such as by methods such as ion exchange, impregnation, coprecipitation, etc., preferably the impregnation method, followed by drying, calcination or without calcination.

[0032] In one embodiment of the present invention, the conditions for drying and calcination are: the drying temperature is 80-350 °C, preferably 100-300 °C, the drying time is 1-24 hours, preferably 2-12 hours, the calcination temperature is 350-550 °C, preferably 400-500 °C, and the calcination time is 1-10 hours, preferably 2-8 hours.

[0033] According to the method provided by the present invention, the hydrogenation conversion catalyst is used after being sulfided. In one embodiment of the present invention, in order to maintain the sulfided form of the catalyst, sulfur is supplemented in the oil-based raw material, or sulfur is added to the recycled hydrogen.

[0034] In one embodiment of the present invention, the oil-based raw material contains a sulfiding agent, and the content of the sulfiding agent is 0.01%-0.5% by weight. The sulfiding agent can be various sulfur-containing substances that can be gasified under hydrogenation deoxygenation conditions and sulfide the hydrotreating catalyst. In the present invention, the sulfiding agent is selected from one or more of hydrogen sulfide, carbon disulfide, dimethyl disulfide, methyl sulfide, n-butyl sulfide and thiophene.

[0035] In the present invention, there is no restriction on the form of the hydrogenation reactor, and it can be any one of a fixed bed reactor, a fluidized bed reactor and a slurry bed reactor. In one embodiment of the present invention, the hydrogenation reactor is a fixed bed reactor. During the hydrogenation process, a multi-bed layer is adopted and cold hydrogen is injected between the bed layers to control the reaction temperature rise, or recycled oil is used to control the reaction temperature rise.

[0036] For the method provided by the present invention, the oil-based raw material undergoes hydrodeoxygenation and isomerization reaction under the action of the hydrogenation conversion catalyst, and the content of isoparaffins in the obtained diesel fraction is controlled to be not less than 40% by weight. The present invention can directly process the oil-based raw material to obtain a diesel fraction with a low freezing point. Compared with the prior art, the process flow is simplified, and the catalyst has high stability and low cost.

[0037] The diesel fraction prepared by the present invention is sulfur-free, has a low freezing point and a high cetane number. It can be used as diesel, or mixed with fossil-based diesel, or used as an additive to increase the cetane number of diesel. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 It is a schematic diagram of one embodiment of the hydrogenation method for preparing diesel fraction from oil-based raw materials provided by the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0039] The present invention will be further described below in conjunction with the drawings, but the present invention is not limited thereby.

[0040] Figure 1 It is a schematic diagram of one embodiment of the hydrogenation method for preparing diesel fraction from oil-based raw materials provided by the present invention. As Figure 1 shown, the oil-based raw material 1, the supplementary hydrogen 2 and the recycle hydrogen 3 are mixed and then enter the hydrogenation reactor 4. The hydrogenation reactor is filled with a hydrogenation conversion catalyst. In the presence of hydrogen, the oil-based raw material contacts the hydrogenation conversion catalyst and mainly undergoes hydrodeoxygenation and hydroisomerization reactions. The reaction effluent 5 of the hydrogenation reactor enters the high-pressure separator 6. After gas-liquid separation, a hydrogen-rich gaseous material 9, water 7 and a liquid hydrocarbon 8 are obtained; the hydrogen-rich gaseous material 9 is pressurized by a compressor 10 and used as the recycle hydrogen 3. The liquid hydrocarbon 8 enters the fractionating tower 11 for fractionation to obtain a low-carbon light hydrocarbon 12, a naphtha fraction 13 and a diesel fraction 14.

[0041] The present invention will be further described below in conjunction with examples, but the present invention is not limited thereby.

[0042] The reagents used in the examples are all pure chemical reagents unless otherwise specified.

[0043] The hydrogenation active component is determined by X-ray fluorescence spectrometry.

[0044] The preparation method of the hydrogenation conversion catalyst C is as follows:

[0045] 234.3 g of CL-1 powder (the alumina obtained by calcining at 500 °C for 4 hours from Changling Catalyst Factory is D1, and its specific surface area and pore distribution are listed in Table 1) and 64.2 g of Siral 40 (from Sasol, SiO 2 39.6%, Al 2 O 3 60.3%, and the XRD characterization shows a pseudo-boehmite phase) are mixed and extruded into a three-leaf shape with an outer diameter of 1.5 mm. The wet strips are dried at 120 °C for 4 hours and calcined at 550 °C for 3 hours to obtain the support S. Take 100 g of the prepared support S and use 125 mL of WO 3A mixed solution of ammonium metatungstate and nickel nitrate with a content of 266.6 g / L and a NiO content of 53.3 g / L was impregnated for 1 hour, then dried at 120 °C for 3 hours and calcined at 450 °C for 3 hours to obtain catalyst C. The properties of alumina D1, support S and catalyst C are shown in Table 1.

[0046] The preparation method of the hydroconversion catalyst DC is as follows:

[0047] 211.2 g of CL-2 powder (the alumina obtained by calcining at 500 °C for 4 hours from Changling Catalyst Factory is D2, and its specific surface area and pore distribution are listed in Table 1), 64.2 g of Siral 40 (from Sasol Company, SiO 2 39.6%, Al 2 O 3 60.3%, and the XRD characterization shows a pseudo-boehmite phase) were mixed and extruded into trilobal bars with an outer circumferential diameter of 1.5 mm. The wet bars were dried at 120 °C for 4 hours and calcined at 550 °C for 3 hours to obtain support DS. Take 100 g of the prepared DS support and impregnate it with 138 mL of a mixed solution of ammonium metatungstate and nickel nitrate with a WO 3 content of 241.5 g / L and a NiO content of 48.3 g / L for 2 hours, then dried at 120 °C for 4 hours and calcined at 450 °C for 2 hours to obtain catalyst DC. The properties of alumina D2, support DS and catalyst DC are shown in Table 1.

[0048] The main properties of the raw materials used in the examples are shown in Table 2.

[0049] Example 1

[0050] 100 mL of the prepared hydroconversion catalyst C was loaded into the hydroconversion reactor. After the catalyst was sulfided, under the conditions of a reaction pressure of 5.0 MPa, a reaction temperature of 360 °C, a liquid hourly space velocity of 1.0 h -1 and a hydrogen-oil volume ratio of 800, palm oil and hydrogen with 0.3 wt% dimethyl disulfide were subjected to a hydroconversion reaction. The obtained reaction product was separated and fractionated to obtain a diesel fraction with a freezing point of 0 °C (boiling range 180 - 324 °C). The content of isoparaffins in the diesel fraction was 40 wt%, the yield of the diesel fraction was 76 wt%, and the cetane number was 85.

[0051] After running for 1000 hours, the reaction conditions were: a reaction pressure of 6.0 MPa, a reaction temperature of 365 °C, a liquid hourly space velocity of 0.5 h -1 and a hydrogen-oil volume ratio of 1200. The obtained diesel fraction (boiling range 175 - 328 °C) had a freezing point of 0 °C, the content of isoparaffins in the diesel fraction was 40 wt%, the yield of the diesel fraction was 75 wt%, and the cetane number was 85.

[0052] Example 2

[0053] 100 mL of the prepared hydroconversion catalyst C was loaded into a hydroconversion reactor. After the catalyst was sulfided, a hydroconversion reaction was carried out with waste cooking oil, hydrogen, and 0.2 wt% of dimethyldisulfide under the conditions of a reaction pressure of 5.0 MPa, a reaction temperature of 370 °C, a liquid hourly space velocity of 1.0 h -1 and a hydrogen-to-oil volume ratio of 800. After the obtained reaction product was separated and fractionated, a diesel fraction with a freezing point of -10 °C (boiling range 170 - 335 °C) was obtained. The content of isoparaffins in the diesel fraction was 60 wt%, the yield of the diesel fraction was 72 wt%, and the cetane number was 80.

[0054] Comparative Example 1

[0055] 100 mL of the prepared hydroconversion catalyst DC was loaded into a hydroconversion reactor. After the catalyst was sulfided, a hydroconversion reaction was carried out with palm oil, hydrogen, and 0.3 wt% of dimethyldisulfide under the conditions of a reaction pressure of 5.0 MPa, a reaction temperature of 360 °C, a liquid hourly space velocity of 1.0 h -1 and a hydrogen-to-oil volume ratio of 800. After the obtained reaction product was separated and fractionated, a diesel fraction with a freezing point of 5 °C (boiling range 180 - 332 °C) was obtained. The content of isoparaffins in the diesel fraction was 32 wt%, the yield of the diesel fraction was 70 wt%, and the cetane number was 78.

[0056] Table 1

[0057]

[0058]

[0059] Table 2

[0060] Item Palm oil Waste cooking oil <![CDATA[Density (20 °C), kg / m 3 > 921.2 918.6 Total acid value, mgKOH / g 0.2 10.2 Oxygen content, % 11.4 11.9 Sulfur content, mg / kg ﹤2.0 5.5 Nitrogen content, mg / kg ﹤2.0 59

Claims

1. A hydrogenation method for preparing diesel fractions from oil and fat raw materials, comprising: The oil and fat raw materials are contacted with a hydroconversion catalyst in the presence of hydrogen for hydroconversion. The oil and fat raw materials are subjected to hydrodeoxygenation and isomerization reactions under the action of the hydroconversion catalyst. After the reaction effluent is subjected to gas-liquid separation, the obtained liquid-phase stream is fractionated to obtain diesel fractions. The content of isoparaffins in the diesel fractions is 40-60% by weight, the initial boiling point of the diesel fractions is 170-205 °C, the final boiling point is 290-350 °C, and the oil and fat raw materials contain a sulfurizing agent with a content of 0.01-0.5% by weight; The hydroconversion catalyst contains a carrier and a hydrogenation active metal component. The carrier is composed of alumina and silica-alumina. Based on the carrier, the content of the alumina is 20-80% by weight, and the content of the silica-alumina is 80-20% by weight. The alumina is an alumina in which the pore volume of pores with a pore diameter less than 60 Å accounts for more than 25% of the total pore volume; the hydrogenation active metal component is at least one selected from Group VIB metal elements and at least one selected from Group VIII metal elements. The Group VIB metal element is molybdenum and / or tungsten, and the Group VIII metal element is cobalt and / or nickel; based on oxides and based on the hydroconversion catalyst, the content of cobalt and / or nickel is 1-10% by weight, and the content of molybdenum and / or tungsten is 5-40% by weight; Reaction conditions for hydroconversion: reaction temperature 250 - 450 °C, pressure 3.0 - 10.0 MPa, liquid hourly space velocity 0.1 - 10 h -1 , hydrogen-oil volume ratio 300 - 2000 Nm 3 / m 3 .

2. The method according to claim 1, wherein, The oil and fat raw materials include one or more of various animal and vegetable oils and fats and waste cooking oil.

3. The method according to claim 1, wherein, The hydroconversion catalyst contains a carrier and a hydrogenation active metal component. The carrier contains alumina and silica-alumina. Based on the carrier, the content of the alumina is 25-75% by weight, and the content of the silica-alumina is 75-25% by weight; The alumina is an alumina in which the pore volume of pores with a pore diameter less than 60 Å accounts for more than 30% of the total pore volume.

4. The method according to claim 1, wherein, The silica-alumina is a silica-alumina having a characteristic X-ray diffraction pattern of γ-alumina. Based on the silica-alumina, the silica-alumina contains 5-60% by weight of silica and 40-95% by weight of alumina.

5. The method according to claim 4, wherein, Based on the silica-alumina, the silica-alumina contains 10-45% by weight of silica and 55-90% by weight of alumina.

6. The method according to claim 1, wherein, Based on oxides and based on the hydroconversion catalyst, the content of cobalt and / or nickel is 2-8% by weight, and the content of molybdenum and / or tungsten is 10-35% by weight.

7. The method according to claim 1, wherein, Reaction conditions for hydroconversion: reaction temperature 300 - 400 °C, pressure 4.0 - 8.0 MPa, liquid hourly space velocity 0.5 - 5 h -1 , hydrogen - to - oil volume ratio is 500 - 1500 Nm 3 / m 3 .

8. The method according to claim 1, wherein, The vulcanizing agent is selected from one or more of H 2 S, CS 2 , dimethyl disulfide, methyl sulfide, n-butyl sulfide, and thiophene.

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