Residue hydrotreating method

Abstract

The present invention relates to the field of residual oil hydroprocessing and discloses a residual oil hydroprocessing method, comprising: contacting a residual oil feedstock with a hydroprotection catalyst, a hydrodemetallization catalyst, and a hydrodesulfurization catalyst in sequence under hydroprocessing conditions; the hydrodesulfurization catalyst is obtained by treating a spent hydroprocessing catalyst. The method comprises: 1) charring and pore-enlarging the spent hydroprocessing catalyst under an oxygen-containing atmosphere; 2) mixing a first leaching agent with the solid product obtained in step 1) for a first leaching; the first leaching agent comprises a polyol; 3) mixing the solid product obtained in the first leaching with a second leaching agent for a second leaching to obtain a leached product; the second leaching agent comprises water and / or ethanol; and 4) subjecting the leached product to low-temperature and high-temperature heat treatments under an oxygen-containing atmosphere; the high-temperature heat treatment temperature is not less than 310°C. This method can improve the utilization rate of spent distillate oil hydroprocessing catalysts and reduce the cost of residual oil hydroprocessing.

Description

Technical Field

[0001] The present invention relates to the field of residual oil hydroprocessing, and in particular to a residual oil hydroprocessing method. Background Art

[0002] At present, domestic refineries unload a large amount of distillate oil hydrogenation catalysts that have been deactivated after the reaction from idle units every year. The main reasons for the deactivation of distillate oil hydrogenation catalysts are coke deposition and metal sintering. For this type of deactivated catalyst, the commonly used regeneration method is to first char the catalyst under certain conditions, and then use a solution containing specific compound components to redisperse the active phase of the charred catalyst.

[0003] CN1921942A reports a method for regenerating a deactivated hydroprocessing catalyst, wherein the hydroprocessing catalyst deactivated due to carbon deposition is first subjected to charcoaling treatment under certain conditions to obtain an intermediate catalyst having a carbon content of 0.5-2.5 wt%. The charcoaled catalyst is then contacted with a nitrogen-containing chelating agent solution and aged, and finally dried to obtain a regenerated catalyst.

[0004] CN106669866A discloses a method for regenerating a deactivated hydrogenation catalyst. The method involves charring the deactivated hydrogenation catalyst, then impregnating the charred catalyst with a solution containing ammonium fluoroborate and 2-amino-1,3-propanediol. The impregnated hydrogenation catalyst is then regenerated after heat treatment. This method can increase the specific surface area of ​​the regenerated catalyst, promote the redispersion of active components, and achieve a high degree of sulfidation of the regenerated hydrogenation catalyst, thereby improving its reaction activity.

[0005] After deactivated distillate hydrogenation catalysts are restored through conventional regeneration methods, they are typically loaded back into the reactor for further industrial use. After one or two regenerations, the catalysts no longer meet the distillate's ultra-deep hydrogenation activity requirements, forcing them to be disposed of as hazardous waste. The high cost and environmental pressure of waste catalyst disposal have become a major challenge for the industry. Domestic refining and petrochemical companies face a long and arduous journey in achieving carbon emission reduction and green development, and the generation of hazardous catalyst waste is detrimental to their sustainable, green development.

[0006] If these waste distillate oil hydroprocessing catalysts that cannot be conventionally regenerated can be treated by special methods and applied to the heavy oil and / or residual oil hydroprocessing reaction process, replacing part of the heavy oil and / or residual oil hydrodesulfurization catalysts, thereby realizing the cascade utilization of waste distillate oil hydroprocessing catalysts, the procurement cost of existing heavy oil and / or residual oil hydroprocessing catalysts can be reduced, and at the same time, the problem of recycling and treating waste distillate oil hydroprocessing catalysts can be solved, which can create significant social and economic benefits. Summary of the Invention

[0007] The purpose of the present invention is to overcome the problem in the prior art that distillate oil hydrogenation catalysts deteriorate in performance after conventional regeneration one to two times, resulting in inability to continue to be used, and to provide a residual oil hydrogenation treatment method. The treatment method can effectively utilize the spent hydrogenation catalyst after regeneration treatment and has a high desulfurization rate.

[0008] During the research process, the inventors of the present invention discovered that when the regenerated catalyst obtained by the existing method of recycling and treating waste distillate oil hydrogenation catalyst is reused in the distillate oil hydrogenation process, after 1-2 regeneration uses, it is difficult to meet the requirements of the distillate oil for the ultra-deep hydrogenation activity of the catalyst. For example, the activity and selectivity of the catalyst cannot fully meet the requirements. At this time, the unloaded catalyst can only be treated as hazardous waste. The high cost of waste catalyst treatment and the great pressure on environmental protection have become a difficult problem that plagues the industry. The inventors of the present invention changed their thinking and treated the waste distillate oil hydrogenation catalyst that does not meet the conventional regeneration conditions through a special method, and used it in the heavy oil and / or residual oil hydrogenation process with slightly lower catalyst requirements. Compared with distillate oil, the compounds in heavy oil and / or residual oil feedstocks have higher molecular weights and larger molecular sizes, and the reaction conditions are more stringent. Therefore, it is necessary to increase the accessibility of the catalyst active centers to the macromolecular compounds in the heavy oil and / or residual oil, improve the diffusion performance of the catalyst pores, and improve the activity stability of the catalyst under harsh reaction conditions. However, the regenerated agent obtained by the conventional regeneration method of waste distillate oil hydrogenation catalyst cannot meet the requirements of heavy oil and / or residual oil hydrogenation reaction.

[0009] The inventors of the present invention use a hydrodesulfurization catalyst obtained by treating a waste hydroprocessing catalyst in combination with a hydroprotection catalyst and a hydrodemetallization catalyst in the hydroprocessing process of residual oil, which not only effectively utilizes the waste hydroprocessing catalyst but also has a higher desulfurization rate.

[0010] In order to achieve the above object, the present invention provides a residual oil hydroprocessing method, which comprises:

[0011] Under hydroprocessing conditions, the residual oil feedstock is contacted with a hydroprotection catalyst, a hydrodemetallization catalyst, and a hydrodesulfurization catalyst in sequence;

[0012] Wherein, the hydrodesulfurization catalyst is obtained by treating a waste hydrogenation catalyst, and the treatment method of the waste hydrogenation catalyst comprises:

[0013] 1) Carburizing and pore-enlarging the spent hydrogenation catalyst in an oxygen-containing atmosphere;

[0014] 2) mixing a first soaking agent with the solid product obtained in step 1) to perform a first soaking; the first soaking agent comprises a polyol;

[0015] 3) mixing the solid product obtained by the first leaching with a second leaching agent, and performing a second leaching to obtain a leached product; the second leaching agent is water and / or ethanol;

[0016] 4) subjecting the leached product to low-temperature heat treatment and high-temperature heat treatment in an oxygen-containing atmosphere; the high-temperature heat treatment temperature is not less than 310° C.

[0017] Preferably, based on the total volume of the hydrogenation protection catalyst, the hydrodemetallization catalyst and the hydrodesulfurization catalyst, the content of the hydrogenation protection catalyst is 5-60 volume %, the content of the hydrodemetallization catalyst is 5-50 volume %, and the content of the hydrodesulfurization catalyst is 10-60 volume %.

[0018] Compared with the prior art, the residue oil hydroprocessing method provided by the present invention can, on the one hand, improve the utilization rate of spent distillate oil hydroprocessing catalysts, and in particular, provide a method for reusing distillate oil hydroprocessing catalysts with high carbon deposits and high deposited impurities; on the other hand, it can effectively reduce the cost of existing residue oil hydroprocessing catalysts. Therefore, the method provided by the present invention has higher economic benefits. DETAILED DESCRIPTION

[0019] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0020] The present invention provides a residual oil hydrotreating method, which comprises:

[0021] Under hydroprocessing conditions, the residual oil feedstock is contacted with a hydroprotection catalyst, a hydrodemetallization catalyst, and a hydrodesulfurization catalyst in sequence;

[0022] Wherein, the hydrodesulfurization catalyst is obtained by treating a waste hydrogenation catalyst, and the treatment method of the waste hydrogenation catalyst comprises:

[0023] 1) Carburizing and pore-enlarging the spent hydrogenation catalyst in an oxygen-containing atmosphere;

[0024] 2) mixing a first soaking agent with the solid product obtained in step 1) to perform a first soaking; the first soaking agent comprises a polyol;

[0025] 3) mixing the solid product obtained by the first leaching with a second leaching agent, and performing a second leaching to obtain a leached product; the second leaching agent is water and / or ethanol;

[0026] 4) subjecting the leached product to low-temperature heat treatment and high-temperature heat treatment in an oxygen-containing atmosphere; the high-temperature heat treatment temperature is not less than 310° C.

[0027] In the present invention, the hydrodesulfurization catalyst is obtained by treating spent hydroprocessing catalysts, further improving the economic efficiency of the overall process. Conventional regeneration processes for spent distillate hydroprocessing catalysts typically involve redispersing the active metals with a solvent and then drying them at low temperatures, without high-temperature calcination. For example, the heat treatment temperature in CN102463127A does not exceed 200°C. This is because the catalyst treated by conventional regeneration methods is still reused in distillate hydroprocessing reactions, where the reaction conditions are relatively milder, and low-temperature drying treatment is beneficial for improving catalyst activity. The present invention, however, aims to regenerate spent distillate hydroprocessing catalysts and apply them to heavy oil / residue hydroprocessing reactions, where the reaction temperatures and pressures are higher and the reaction feedstock properties are poorer, thus requiring catalysts with higher activity and stability. The inventors discovered that a combined low-temperature and high-temperature heat treatment method can improve the activity and stability of the resulting hydroprocessing catalyst under harsh reaction conditions. When used in conjunction with a hydroprotected catalyst and a hydrodemetallization catalyst in the hydroprocessing of residual oil, this not only effectively utilizes the spent hydroprocessing catalyst but also achieves a higher desulfurization rate.

[0028] In the present invention, "residue oil" refers to the component remaining at the bottom of the distillation tower when crude oil is distilled, including atmospheric residue oil and vacuum residue oil. The method provided by the present invention is applicable to the hydrotreatment of various residue oils. Preferably, the density of the residue oil is 920-1050 kg / m 3 ; The residual carbon content is less than 15 weight%; The sulfur content is less than 5 weight%.

[0029] The method provided by the present invention can be carried out in a conventional residue hydroprocessing unit, and the present invention is not particularly limited to this. For example, a hydroprotection catalyst, a hydrodemetallization catalyst, and a hydrodesulfurization catalyst can be sequentially loaded into the residue hydroprocessing unit along the direction of the material flow. The residue hydroprocessing unit is preferably a fixed-bed hydroprocessing unit. Furthermore, the various catalysts of the present invention can be loaded into the same fixed-bed hydroprocessing unit or separately loaded into multiple fixed-bed hydroprocessing units connected in series. As long as the catalyst loading method complies with the requirements of the present invention, there is no particular limitation on the number of fixed-bed hydroprocessing units.

[0030] According to the present invention, in order to further improve the desulfurization rate of residual oil treatment, preferably, based on the total volume of the hydroprotection catalyst, the hydrodemetallization catalyst and the hydrodesulfurization catalyst, the content of the hydroprotection catalyst is 5-60 volume %, preferably 10-50 volume %, more preferably 15-30 volume %, the content of the hydrodemetallization catalyst is 5-50 volume %, preferably 10-40 volume %, more preferably 20-40 volume %, and the content of the hydrodesulfurization catalyst is 10-60 volume %, preferably 20-55 volume %, more preferably 40-55 volume %.

[0031] In the present invention, preferably, the active metal component content in the hydrodesulfurization catalyst is not less than 18% in terms of oxides based on the total weight of the fresh catalyst corresponding to the hydrodesulfurization catalyst; and the deposited impurity content in the hydrodesulfurization catalyst is not more than 2% in terms of oxides based on the total weight of the hydrodesulfurization catalyst. The method for treating spent hydrodesulfurization catalyst provided by the present invention has excellent treatment effects on spent hydrodesulfurization catalysts with high carbon deposits and high deposited impurities. Among existing treatment methods, a commonly used regeneration method is to first char the catalyst under certain conditions, and then use a solution containing specific compound components to redisperse the active phase of the charred catalyst. For example, CN111821998A discloses impregnation of the charred catalyst with C1-C20 organic alcohols, organic acids, organic amines, and organic ammonium salts. CN111822060A discloses two-stage charring and pore expansion, followed by impregnation with a solution containing a phosphorus compound. The purpose of both methods is to redisperse the active phase and improve the dispersion of active metals. However, the inventors of the present invention have discovered that while this saturated or unsaturated impregnation method can improve the dispersion of the active phase, it cannot remove inactive deposited impurities from the spent hydroprocessing catalyst. Compared to existing treatment methods, the treatment method provided by the present invention can effectively remove carbon deposits and deposited impurities from spent hydroprocessing catalysts while ensuring that the resulting hydrodesulfurization catalyst maintains a high content of active metal components. The resulting hydrodesulfurization catalyst, when used in conjunction with a hydroprotected catalyst and a hydrodemetallization catalyst in the hydroprocessing of residual oil, exhibits a high desulfurization rate.

[0032] The term "the total weight of the fresh catalyst corresponding to the hydrodesulfurization catalyst is taken as the basis" in the present invention means that the active metal component content is based on the fresh catalyst, that is, the deposited impurities and carbon in the catalyst are not included in the total amount.

[0033] In the present invention, unless otherwise specified, the carbon content is determined by extracting the catalyst with toluene using a carbon-sulfur analyzer, and the deposited impurity content is determined by calcining the catalyst at 600° C. in air for 3 hours using X-ray fluorescence spectrometry.

[0034] According to the present invention, preferably, the specific surface area of ​​the hydrodesulfurization catalyst is 80-300m 2 / g, pore volume is 0.2-1.3mL / g, and the most probable pore diameter is 5-14nm. More preferably, the specific surface area of ​​the hydrodesulfurization catalyst is 90-280m 2 / g, pore volume is 0.25-1.1mL / g, and the most probable pore diameter is 7-14nm. In the above preferred case, it is helpful to further improve the desulfurization effect of residual oil hydrotreatment.

[0035] In the present invention, the first and second leaching are carried out in sequence, which can effectively remove impurities deposited on the spent hydrogenation catalyst during the reaction and some aggregated low-activity metal components, thereby achieving the purpose of unblocking the pores and increasing the pore volume of the catalyst.

[0036] According to the present invention, the first impregnating agent includes a polyol, and the second impregnating agent is water and / or ethanol. The use of a combination of the above impregnating agents for synergistic impregnation is more conducive to improving the desulfurization performance of the obtained hydrogenation catalyst.

[0037] In order to further improve the immersion effect, preferably, the general formula of the polyol is C n H 2n+2-x (OH) x , wherein n=2-5, x=2-3, preferably, the polyol is ethylene glycol and / or glycerol.

[0038] Preferably, the first impregnating agent also contains water, and the concentration of the first impregnating agent is 0.01-4 mol / L, preferably 0.01-2 mol / L. Within the above preferred concentration range, it is helpful to selectively remove impurities deposited on the catalyst during the reaction and aggregated low-activity metal components. If the concentration of the first impregnating agent is too high, it may cause excessive removal of dispersed high-activity metal components on the catalyst.

[0039] According to the present invention, during actual operation, the immersion conditions can be adjusted according to the physical and chemical properties of the catalyst after carbonization and pore expansion. The principle is to remove as many impurities as possible that are deposited on the catalyst during the reaction, as well as the metal components with low activity in the aggregated state, while retaining as many metal components with high activity in the dispersed state as possible on the catalyst.

[0040] According to the present invention, preferably, in step 2), the volume ratio of the first soaking agent to the solid product obtained in step 1) is 1-5:1, preferably 3-5:1.

[0041] The first and second leaching can be performed in conventional manners, such as soaking the solid product in a leaching agent and then performing solid-liquid separation. The solid-liquid separation can be performed using conventional operations in the art, and the present invention is not particularly limited thereto.

[0042] Preferably, the first soaking time is 0.5-10 hours, preferably 1-5 hours. It can be understood that the first soaking time refers to the soaking time of the solid product in the first soaking agent.

[0043] According to the present invention, preferably, the first immersion is carried out under stirring conditions. Preferably, the stirring rate is 30-600 rpm, preferably 50-300 rpm. The adoption of the above preferred embodiment is conducive to improving the effect of the first immersion and improving the catalytic activity of the treated hydrodesulfurization catalyst.

[0044] According to the present invention, preferably, the volume ratio of the second soaking agent to the solid product obtained by the first soaking is 1-6:1, preferably 2-5:1.

[0045] Preferably, the second immersion time is 0.1-2 hours, preferably 0.5-2 hours. It is understood that the second immersion time refers to the immersion time of the solid product obtained from the first immersion in the second immersion agent.

[0046] In the present invention, the specific method of the charring and pore-enlarging treatment in step 1) is not particularly limited and can be carried out in a conventional manner in the art, which is well known to those skilled in the art. Preferably, in order to further improve the catalytic activity of the hydrogenation catalyst, the charring and pore-enlarging treatment includes optional stages (1) and (2), wherein the conditions of stage (1) include: a temperature of 200-500° C. and a time of 1-10 hours, and the conditions of stage (2) include: a temperature of 500-850° C. and a time of 1-10 hours.

[0047] Preferably, the conditions of stage (1) include: temperature of 230-450°C, and time of 1-8 hours. Preferably, the conditions of stage (2) include: temperature of 600-800°C, preferably 600-750°C, and time of 1-8 hours, preferably 1-4 hours.

[0048] In the present invention, preferably, the conditions of stage (1) include: treating at a temperature of 230-280°C for 1-3 hours, and then treating at 350-450°C for 1-4 hours; adopting the above preferred embodiment, in conjunction with subsequent immersion and heat treatment, is conducive to further improving the pore volume and most probable pore diameter of the hydrodesulfurization catalyst. The hydrodesulfurization catalyst obtained under such preferred carbonization and pore expansion treatment conditions increases the accessibility of the catalyst active center to macromolecular compounds in heavy oil and / or residual oil, and at the same time improves the diffusion performance of the catalyst pores. When the obtained hydrodesulfurization catalyst is used in the heavy oil and / or residual oil hydrotreatment process, better desulfurization and residual carbon removal effects can be achieved.

[0049] The charcoal burning and pore enlargement treatment of the present invention can be carried out in conventional equipment, as long as step 1) can be carried out in an oxygen-containing atmosphere under the optional conditions of stage (1) and stage (2). For example, the charcoal burning and pore enlargement treatment can be carried out in a muffle furnace.

[0050] According to the present invention, in step 1), the oxygen-containing atmosphere provides oxygen for the charcoal burning treatment of the spent hydrogenation catalyst. The present invention has a wide range of selection for the content of oxygen in the oxygen-containing atmosphere. For example, the volume content of oxygen in the oxygen-containing atmosphere can be 8-30%, preferably 10-25%. The oxygen-containing atmosphere of the present invention can be provided by different methods according to different requirements of the volume content of oxygen. For example, the oxygen-containing atmosphere can be provided by air. When the oxygen content of the oxygen-containing atmosphere is required to be high, the oxygen-containing atmosphere can be provided by air and oxygen. When the oxygen content of the oxygen-containing atmosphere is required to be low, the oxygen-containing atmosphere can be provided by air and an inert atmosphere (for example, nitrogen). In the embodiment of the present invention, the use of air to provide the oxygen-containing atmosphere is used as an example for illustrative description. Using air to provide the oxygen-containing atmosphere is more conducive to cost saving, but the present invention is not limited to this.

[0051] In the present invention, the heat treatment includes low-temperature heat treatment and high-temperature heat treatment. In the conventional regeneration process of waste distillate oil hydrogenation catalyst, the active metal is redispersed with a solvent and then usually dried only at low temperature without high-temperature calcination. This is because the catalyst treated by the conventional regeneration method is still reused in the distillate oil hydrogenation reaction, and its reaction conditions are relatively milder. Low-temperature drying treatment is conducive to improving catalyst activity. The purpose of the present invention is to apply the regenerated waste distillate oil hydrogenation catalyst to heavy oil / residue oil hydrogenation reaction, which has higher reaction temperature and pressure and worse reaction raw material properties. Therefore, the catalyst needs to have higher activity and stability. The inventors found in their research that the activity and stability of the hydrodesulfurization catalyst under harsh reaction conditions can be improved by combining low-temperature heat treatment and high-temperature heat treatment.

[0052] In the present invention, the selection range of the oxygen-containing atmosphere in step 4) is the same as that in step 1), and will not be repeated here.

[0053] Preferably, the conditions of the low-temperature heat treatment include: a temperature of 70-200° C., preferably 80-150° C., and a time of 2-10 hours, preferably 3-6 hours.

[0054] Preferably, the high temperature heat treatment conditions include: a temperature of 310-550° C., preferably 351-520° C., and a time of 1-10 hours, preferably 2-8 hours. The above preferred embodiment is conducive to further improving the catalytic activity of the hydrodesulfurization catalyst after treatment.

[0055] In the present invention, a waste hydrogenation catalyst refers to a catalyst whose performance (which may include at least one of activity, selectivity and stability) deteriorates after use. It includes both discarded hydrogenation catalysts that cannot meet the hydrogenation activity requirements after long-term recycling even after regeneration by existing means, and used hydrogenation catalysts that can continue to be used after regeneration by existing means. The waste hydrogenation catalyst can be various hydrogenation catalysts conventionally used for various oil products in the field, and the present invention has no particular limitation on this. According to a specific embodiment of the present invention, the waste hydrogenation catalyst of the present invention includes but is not limited to at least one of a waste gasoline hydrogenation catalyst, a waste diesel hydrogenation catalyst, a waste kerosene hydrogenation catalyst and a waste wax oil hydrogenation catalyst. The embodiments of the present invention are illustratively described using a waste diesel hydrogenation catalyst as an example.

[0056] According to the present invention, preferably, the spent hydrogenation catalyst comprises a carrier and an active metal component supported on the carrier, and the active metal component comprises molybdenum and / or tungsten and nickel and / or cobalt.

[0057] The present invention provides a relatively broad range of molybdenum and / or tungsten, as well as nickel and / or cobalt content. These ranges can be adjusted by those skilled in the art based on practical circumstances. More preferably, the molybdenum and / or tungsten content, calculated as oxides, is 10-40% by weight, and the nickel and / or cobalt content is 1.5-8% by weight, based on the total amount of fresh catalyst corresponding to the spent hydrogenation catalyst. Conventional ranges for the active metal components, molybdenum and / or tungsten, and nickel and / or cobalt, in waste gasoline hydrogenation catalysts, waste diesel hydrogenation catalysts, waste kerosene hydrogenation catalysts, and waste wax oil hydrogenation catalysts may vary. These ranges can be selected by those skilled in the art using conventional methods, and the present invention will not further elaborate on these ranges.

[0058] It should be noted that, in addition to the carrier and the active metal components supported on the carrier, the spent hydrogenation catalyst also includes deposited impurities and carbon deposited after long-term recycling. The "total amount of fresh catalyst corresponding to the spent hydrogenation catalyst is used as a benchmark" in the present invention means that the content of molybdenum and / or tungsten and the content of nickel and / or cobalt are based on the fresh catalyst, that is, the above-mentioned deposited impurities and carbon are not included. Since the spent hydroprocessing catalyst has the characteristics of high carbon deposits and / or deposited impurities (such as iron, calcium, sodium, silicon) compared to the fresh agent, the deposited impurities come from the raw oil. Therefore, the present invention uses the carbon content and / or deposited impurity content to indicate whether the catalyst is a spent hydrogenation catalyst. Generally, the carbon content and deposited impurity content of the fresh agent are basically 0, while the carbon content of the spent hydrogenation catalyst can be as high as 30% by weight, and the deposited impurity content can be as high as 20% by weight. In the prior art, the treatment of non-hydrogenation catalysts often focuses on the amount of carbon deposits, while ignoring the deposited impurities in the spent hydrogenation catalyst. Such metal impurities cannot be removed by conventional methods such as roasting. The inventors of the present invention have discovered through continuous experimental research that by sequentially performing the first and second leachings, the impurities deposited on the spent hydrogenation catalyst during the reaction and some aggregated low-activity metal components can be effectively removed, thereby further improving the activity of the hydrodesulfurization catalyst and improving the residue oil hydrotreatment effect.

[0059] According to a preferred embodiment of the present invention, based on the total weight of the spent hydrogenation catalyst, the carbon content of the spent hydrogenation catalyst is less than 30%, and the deposited impurity content is less than 20%. Preferably, the carbon content of the spent hydrogenation catalyst is less than 15%, and the deposited impurity content is less than 10%. Further preferably, the carbon content of the spent hydrogenation catalyst is 5-13%, and the deposited impurity content is 1-8%.

[0060] The inventors of the present invention have found that, preferably, a hydrodesulfurization catalyst obtained by treating a spent hydroprocessing catalyst that meets the above-mentioned physicochemical characteristics and used in residue oil hydroprocessing has higher desulfurization performance.

[0061] The inventors of the present invention have also discovered that using spent hydrogenation catalyst with a particle size of 10-30 mesh, preferably 14-20 mesh, and more preferably 16-20 mesh, can further improve the desulfurization performance of the resulting hydrodesulfurization catalyst. Prior to use, the spent hydrogenation catalyst can be sieved to obtain a spent hydrogenation catalyst meeting the aforementioned preferred particle size requirements. Therefore, the method provided herein preferably further includes sieving the spent hydrogenation catalyst prior to step 1).

[0062] The hydrogenation protection catalyst and the hydrodemetallization catalyst of the present invention can be independently various hydrogenation protection catalysts and hydrodemetallization catalysts conventionally used in the art, and the present invention has no particular limitation thereto.

[0063] The hydrogenation protection catalyst of the present invention may not contain an active metal component. Preferably, the hydrogenation protection catalyst and the hydrodemetallization catalyst each independently contain a carrier and an active metal component supported on the carrier, wherein the active metal component is selected from at least one of Group VIB and / or Group VIII metal elements. Preferably, the Group VIB metal element is molybdenum and / or tungsten, and the Group VIII metal element is nickel and / or cobalt. More preferably, the active metal component is any one or more of a combination of nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum, and cobalt-molybdenum.

[0064] The supports of the hydroprotected catalyst and the hydrodemetallization catalyst of the present invention can each be independently selected from at least one of aluminum oxide, silicon oxide, and titanium oxide. Other elements such as boron, germanium, zirconium, phosphorus, chlorine, or fluorine can also be added to the supports for modification.

[0065] According to the present invention, preferably, in the hydrogenation protection catalyst, the content of active metal components is 1-15 weight % in terms of oxides, based on the total amount of the hydrogenation protection catalyst; specifically, the content of molybdenum and / or tungsten is not higher than 10 weight %, and the content of nickel and / or cobalt is not higher than 5 weight %.

[0066] In the present invention, the hydrogenation protection catalyst can be an industrial agent or can be prepared by existing methods. For example, the hydrogenation protection catalyst can be at least one of the RG series catalysts developed by the Petrochemical Research Institute of Sinopec.

[0067] According to the present invention, preferably, in the hydrodemetallization catalyst, the content of active metal components, calculated as oxides, based on the total amount of the hydrodemetallization catalyst is 6-20 wt %; specifically, the content of molybdenum and / or tungsten is not higher than 15 wt %, and the content of nickel and / or cobalt is not higher than 6 wt %.

[0068] In the present invention, the hydrodemetallization catalyst can be an industrial catalyst or can be prepared by existing methods. The hydrodemetallization catalyst can be, for example, at least one of the RDM series catalysts and RUF series catalysts developed by the Petrochemical Research Institute of Sinopec.

[0069] According to the present invention, the method is carried out under hydrotreatment conditions. Preferably, the hydrotreatment conditions include: temperature of 320-450°C, hydrogen partial pressure of 8-20 MPa, liquid hourly volume space velocity of 0.1-1 h -1 , the hydrogen-oil volume ratio is 500-1500; further preferably, the conditions of the hydrotreatment include: temperature of 350-420 ° C, hydrogen partial pressure of 12-18 MPa, liquid hourly volume space velocity of 0.2-0.6h-1 , the hydrogen to oil volume ratio is 800-1200. In the present invention, unless otherwise specified, the hydrogen partial pressure refers to the gauge pressure.

[0070] The present invention will be described in detail below through examples.

[0071] In the following preparation examples, the specific surface area, pore volume and most probable pore diameter were measured using the low-temperature nitrogen adsorption method.

[0072] The carbon content in the catalyst was determined by a carbon-sulfur analyzer.

[0073] The composition of the catalyst was determined by X-ray fluorescence spectrometry (XRF). The specific method is shown in the petrochemical analysis method RIPP133-90.

[0074] The following preparation example is used to illustrate the treatment of spent hydrogenation catalyst to obtain a hydrodesulfurization catalyst.

[0075] Preparation Example 1

[0076] 1) An industrial deactivated diesel hydrogenation catalyst (carbon content: 10.26 wt%, content of deposited impurities such as iron, sodium, and vanadium: 7.5 wt%, NiMo / Al2O3; Ni content: 4.6 wt%, Mo content: 27.8 wt%, calculated as oxides, based on the total amount of fresh catalyst corresponding to the spent hydrogenation catalyst), referred to as deactivator A, was sieved to obtain a 16-20 mesh deactivator A, which was placed in a muffle furnace and subjected to a programmed temperature-raising charcoaling and pore-expanding treatment in an air atmosphere, comprising: stage 1) maintaining the temperature at 250°C for 1 hour, maintaining the temperature at 350°C for 2 hours, and then performing stage 2) maintaining the temperature at 650°C for 2 hours, to obtain catalyst B;

[0077] 2) At room temperature, with a stirring rate of 120 rpm, the catalyst B obtained in step 1) was first soaked with a 1.5 mol / L glycerol aqueous solution, wherein the volume of the glycerol aqueous solution used was 3 times the volume of the catalyst, and the soaking time was 2 hours, followed by solid-liquid separation;

[0078] 3) performing a second immersion of the solid product obtained in step 2) with deionized water at room temperature, wherein the volume of the deionized water used is 4 times the volume of the solid, and the immersion time is 1 hour, followed by solid-liquid separation to obtain a washed product;

[0079] 4) The washed product was heat treated, first at 120°C for 3 hours in an air atmosphere, which was designated as Catalyst C; and then Catalyst C was heat treated at 410°C for 5 hours in an air atmosphere to obtain Catalyst D.

[0080] Preparation Example 2

[0081] 1) Catalyst B was obtained according to the method of Preparation Example 1;

[0082] 2) At room temperature, at a stirring rate of 180 rpm, the catalyst B obtained in step 1) was first soaked in a 1 mol / L ethylene glycol aqueous solution, wherein the volume of the ethylene glycol aqueous solution used was 4 times the volume of the catalyst, and the soaking time was 5 hours, followed by solid-liquid separation;

[0083] 3) performing a second immersion of the solid product obtained in step 2) with ethanol at room temperature, wherein the volume of the ethanol used is 3 times the volume of the solid, and the immersion time is 1.5 hours, followed by solid-liquid separation to obtain a washed product;

[0084] 4) The washed product was heat treated, first at 100°C for 4 hours in an air atmosphere, and then at 410°C for 4 hours in an air atmosphere, to obtain Catalyst E.

[0085] Preparation Example 3

[0086] The method of Preparation Example 1 was followed, except that in step 1), the charring and pore-enlarging treatment included: stage 1) maintaining the temperature at 350° C. for 2 hours, followed by stage 2) maintaining the temperature at 650° C. for 2 hours, to obtain Catalyst F;

[0087] The first impregnation, the second impregnation and the heat treatment were carried out in the same manner as in Preparation Example 1 to obtain Catalyst G.

[0088] Preparation Example 4

[0089] 1) Catalyst B was obtained according to the method of Preparation Example 1;

[0090] 2) At room temperature, with a stirring rate of 45 rpm, the catalyst B obtained in step 1) was first soaked in a 0.2 mol / L glycerol aqueous solution, wherein the volume of the glycerol aqueous solution used was 0.8 times the volume of the catalyst, and the soaking time was 10 minutes, followed by solid-liquid separation;

[0091] 3) performing a second immersion of the solid product obtained in step 2) with deionized water at room temperature, wherein the volume of the deionized water used is 1.5 times the volume of the solid, and the immersion time is 5 minutes, followed by solid-liquid separation to obtain a washed product;

[0092] 4) The above-mentioned leached product was heat-treated in the same manner as in Preparation Example 1 to obtain Catalyst H.

[0093] Preparation Example 5

[0094] 1) Catalyst B was obtained according to the method of Preparation Example 1;

[0095] 2) At room temperature, with a stirring rate of 350 rpm, the catalyst B obtained in step 1) was first soaked in a 5 mol / L glycerol aqueous solution, wherein the volume of the glycerol aqueous solution used was 6 times the volume of the catalyst, and the soaking time was 12 hours, followed by solid-liquid separation;

[0096] 3) performing a second immersion of the solid product obtained in step 2) with deionized water at room temperature, wherein the volume of the deionized water used is 7 times the volume of the solid, and the immersion time is 3 hours, followed by solid-liquid separation to obtain a washed product;

[0097] 4) The above-mentioned leached product was heat-treated in the same manner as in Preparation Example 1 to obtain Catalyst I.

[0098] Preparation Example 6

[0099] The method of Preparation Example 1 is followed, except that the charcoaling treatment in step 1) includes: constant temperature at 250° C. for 1 hour and constant temperature at 410° C. for 3 hours, to obtain charcoaled catalyst J;

[0100] The first impregnation, the second impregnation and the heat treatment were carried out in the same manner as in Preparation Example 1 to obtain Catalyst K.

[0101] Preparation Example 7

[0102] The method of Preparation Example 1 was followed, except that the conditions for the first immersion in step 2) did not include stirring. The second immersion and heat treatment were performed in the same manner as in Preparation Example 1 to obtain Catalyst L.

[0103] Comparative Preparation Example 1

[0104] 1) Catalyst B was obtained according to the method of Preparation Example 1;

[0105] 2) At room temperature, with a stirring rate of 120 rpm, soaking the catalyst B obtained in step 1) in a 1.5 mol / L glycerol aqueous solution, wherein the volume of the glycerol aqueous solution used is 3 times the volume of the catalyst, for 2 hours, followed by solid-liquid separation to obtain a soaked product;

[0106] 3) The above-mentioned leached product was heat-treated in the same manner as in Preparation Example 1 to obtain Catalyst M.

[0107] Comparative Preparation Example 2 (Conventional Regeneration Method)

[0108] 1) Obtain charcoaled catalyst J according to the method of Preparation Example 6;

[0109] 2) An aqueous solution of glycerol was prepared and impregnated with Catalyst J by an equal volume saturation impregnation method. The mixture was sealed and placed at room temperature (25°C) for 3 hours, wherein the mass ratio of Catalyst J to glycerol was 8.7. The mixture was then dried at 120°C in an air atmosphere for 3 hours to obtain Catalyst N.

[0110] Comparative Preparation Example 3

[0111] 1) An industrial deactivated diesel hydrogenation catalyst (carbon content: 10.26 wt%, content of deposited impurities such as iron, sodium, and vanadium: 7.5 wt%, NiMo / Al2O3; Ni content: 4.6 wt%, Mo content: 27.8 wt%, calculated as oxides, based on the total amount of fresh catalyst corresponding to the spent hydrogenation catalyst) was taken, referred to as deactivator A, and sieved to obtain a 16-20 mesh deactivator A. The deactivator A was first soaked in a 1.5 mol / L glycerol aqueous solution at room temperature with a stirring rate of 120 rpm, wherein the volume of the glycerol aqueous solution used was three times the volume of the catalyst, for a soaking time of 2 hours, followed by solid-liquid separation;

[0112] 2) washing the solid product obtained in step 1) with deionized water at room temperature for a second time, wherein the volume of the deionized water used is 4 times the volume of the solid product, and the soaking time is 1 hour, followed by solid-liquid separation;

[0113] 3) The solid product obtained in step 2) was heat treated, first at 120 ° C. for 3 hours in an air atmosphere, and then placed in a muffle furnace for high-temperature treatment in an air atmosphere by programmed temperature increase, with the conditions of constant temperature at 250 ° C. for 3 hours and constant temperature at 410 ° C. for 4 hours to obtain catalyst O.

[0114] Comparative Preparation Example 4

[0115] 1) Catalyst B was obtained according to the method of Preparation Example 1;

[0116] 2) At room temperature, with a stirring rate of 120 rpm, the catalyst B obtained in step 1) was first soaked with a 1.5 mol / L oxalic acid solution, wherein the volume of the oxalic acid solution used was 3 times the volume of the catalyst, and the soaking time was 2 hours, followed by solid-liquid separation;

[0117] 3) soaking the solid product obtained in step 2) in deionized water at room temperature, wherein the volume of the deionized water used is 4 times the volume of the solid, and the soaking time is 1 hour, followed by solid-liquid separation to obtain a washed product;

[0118] 4) The above-mentioned leached product was heat-treated in the same manner as in Preparation Example 1 to obtain Catalyst P.

[0119] The physicochemical properties of the deactivator A and catalyst BP in the above preparation example are listed in Table 1.

[0120] Table 1

[0121]

[0122]

[0123] Table 1 lists the basic physicochemical properties of catalysts A and B. Deactivator A exhibits high carbon content and deposited impurities, resulting in clogged reaction pores and a relatively small pore volume and most probable pore diameter. Compared to deactivator A, catalyst B, after charring and pore expansion, exhibits reduced carbon content and significantly increased pore volume and most probable pore diameter. Furthermore, selective removal of deposited impurities and some aggregated low-activity metal components further increases the pore volume and most probable pore diameter of catalysts C, D, and E. Furthermore, if the proportion of deposited impurities removed is too low, as in catalyst H, further increases in the catalyst's pore volume and most probable pore diameter are unlikely. If the proportion of deposited impurities removed is too high, as in catalyst I, some of the active metal components in the catalyst are also removed.

[0124] The following examples are used to illustrate the residual oil hydroprocessing method provided by the present invention.

[0125] Example

[0126] The atmospheric residue of crude oil imported from the Middle East (its properties are listed in Table 2, the same below) and hydrogen were introduced into a fixed-bed hydrogenation reactor and sequentially contacted with the catalyst loaded therein for hydrogenation treatment. The total loading volume of the catalyst in the fixed-bed hydrogenation reactor was 500 mL. Along the logistics direction, the fixed-bed hydrogenation reactor was sequentially loaded with a hydrogenation protection catalyst, a hydrodemetallization catalyst, and a hydrodesulfurization catalyst according to the volume contents in Table 3. The conditions for the hydrotreatment included: a reaction temperature of 380°C, a hydrogen partial pressure of 14 MPa, and a liquid hourly space velocity of 0.5 h -1 , hydrogen-oil volume ratio 600:1.

[0127] The hydroprotected catalyst was RG-30B, developed by the Sinopec Research Institute of Petrochemicals. The hydrodemetallization catalyst was RDM-32, developed by the Sinopec Research Institute of Petrochemicals. The hydrodesulfurization catalysts were the hydrodesulfurization catalyst and a reference agent, respectively, prepared in the above-mentioned preparation example. The reference agent was a residual oil hydrodesulfurization catalyst (NiMo / Al2O3, with a Ni content of 3.0 wt% and a Mo content of 15.4 wt% as oxides) developed by the Sinopec Research Institute of Petrochemicals. The desulfurization performance of the different hydrodesulfurization catalysts was compared, and the results are listed in Table 3.

[0128] The specific calculation method of desulfurization rate is as follows:

[0129]

[0130] Table 2

[0131]

[0132]

[0133] Table 3

[0134]

[0135]

[0136] As can be seen from the results in Table 3, the residue oil hydroprocessing method provided by the present invention not only effectively utilizes the spent hydrogenation catalyst but also maintains a relatively high residue oil hydrodesulfurization rate. This not only improves the utilization rate of the spent distillate oil hydrogenation catalyst but also effectively reduces the cost of existing residue oil hydrogenation catalysts. The method provided by the present invention has higher economic benefits.

[0137] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A residual oil hydrotreating method, the method comprising: Under hydroprocessing conditions, the residual oil feedstock is contacted with a hydroprotection catalyst, a hydrodemetallization catalyst, and a hydrodesulfurization catalyst in sequence; Wherein, the hydrodesulfurization catalyst is obtained by treating a waste hydrogenation catalyst, and the treatment method of the waste hydrogenation catalyst comprises: 1) In an oxygen-containing atmosphere, the spent hydrogenation catalyst is subjected to carbonization and pore expansion treatment; 2) mixing a first soaking agent with the solid product obtained in step 1) to perform a first soaking; The first soaking comprises soaking the solid product in a first soaking agent and then performing solid-liquid separation; The first soaking agent is composed of polyol and water, and the concentration of the polyol aqueous solution is 1-2 mol / L; The volume ratio of the first soaking agent to the solid product obtained in step 1) is 3-5:1; 3) mixing the solid product obtained from the first leaching with a second leaching agent, and performing a second leaching to obtain a leached product; the second leaching comprises immersing the solid product in the second leaching agent, and then performing solid-liquid separation; the second leaching agent is water and / or ethanol; 4) subjecting the leached product to low-temperature heat treatment and high-temperature heat treatment in an oxygen-containing atmosphere; the high-temperature heat treatment temperature is not less than 310°C.

2. The method according to claim 1, wherein Based on the total volume of the hydrogenation protection catalyst, the hydrodemetallization catalyst and the hydrodesulfurization catalyst, the content of the hydrogenation protection catalyst is 5-60 volume %, the content of the hydrodemetallization catalyst is 5-50 volume %, and the content of the hydrodesulfurization catalyst is 10-60 volume %.

3. The method according to claim 2, wherein: Based on the total volume of the hydrogenation protection catalyst, the hydrodemetallization catalyst and the hydrodesulfurization catalyst, the content of the hydrogenation protection catalyst is 10-50 volume %, the content of the hydrodemetallization catalyst is 10-40 volume %, and the content of the hydrodesulfurization catalyst is 20-55 volume %.

4. The method according to claim 3, wherein: Based on the total volume of the hydrogenation protection catalyst, the hydrodemetallization catalyst and the hydrodesulfurization catalyst, the content of the hydrogenation protection catalyst is 15-30 volume %, the content of the hydrodemetallization catalyst is 20-40 volume %, and the content of the hydrodesulfurization catalyst is 40-55 volume %.

5. The method according to any one of claims 1 to 4, wherein: Based on the total weight of the fresh catalyst corresponding to the hydrodesulfurization catalyst, the content of active metal components in the hydrodesulfurization catalyst is not less than 18% in terms of oxides; based on the total weight of the hydrodesulfurization catalyst, the content of deposited impurities in the hydrodesulfurization catalyst is not more than 2% in terms of oxides, and the content of deposited impurities is determined by calcining the hydrodesulfurization catalyst at 600° C. in air for 3 hours and then measuring it by X-ray fluorescence spectrometry.

6. The method according to any one of claims 1 to 4, wherein: The specific surface area of ​​the hydrodesulfurization catalyst is 80-300m 2 / g, the pore volume is 0.2-1.3mL / g, and the most probable pore diameter is 5-14nm.

7. The method according to any one of claims 1 to 4, wherein: The specific surface area of ​​the hydrodesulfurization catalyst is 90-280m 2 / g, the pore volume is 0.25-1.1mL / g, and the most probable pore diameter is 7-14nm.

8. The method according to any one of claims 1 to 4, wherein: In the method for treating the spent hydrogenation catalyst, the general formula of the polyol is C n H 2n+2-x (OH) x , where n=2-5, x=2-3.

9. The method according to claim 8, wherein The polyol is ethylene glycol and / or glycerol.

10. The method according to any one of claims 1 to 4, wherein: The time of the first immersion is 0.5-10 hours.

11. The method according to any one of claims 1 to 4, wherein: The first immersion is performed under stirring conditions, and the stirring rate is 30-600 rpm.

12. The method according to claim 11, wherein The first immersion is performed under stirring conditions, and the stirring rate is 50-300 rpm.

13. The method according to any one of claims 1 to 4, wherein: The second immersion time is 0.1-2 hours.

14. The method according to any one of claims 1 to 4, wherein: The conditions of the low-temperature heat treatment include: a temperature of 70-200° C. and a time of 2-10 hours.

15. The method according to claim 14, wherein The conditions of the low-temperature heat treatment include: a temperature of 80-150° C. and a time of 3-6 hours.

16. The method according to any one of claims 1 to 4, wherein: The conditions of the high temperature heat treatment include: a temperature of 310-550° C. and a time of 1-10 hours.

17. The method according to claim 16, wherein The conditions of the high temperature heat treatment include: a temperature of 351-520° C. and a time of 2-8 hours.

18. The method according to any one of claims 1 to 4, wherein: The charcoal burning and pore expansion treatment includes stage (1) and stage (2). The conditions of stage (1) include: temperature of 200-500°C and time of 1-10 hours. The conditions of stage (2) include: temperature of 500-850°C and time of 1-10 hours.

19. The method according to claim 18, wherein The conditions of the stage (1) include: temperature of 230-450°C and time of 1-8 hours.

20. The method according to claim 19, wherein The conditions of the stage (1) include: treating at a temperature of 230-280°C for 1-3 hours, and then treating at 350-450°C for 1-4 hours.

21. The method according to claim 18, wherein The conditions of the stage (2) include: a temperature of 600-800° C.; and a time of 1-8 hours.

22. The method according to claim 18, wherein The conditions of the stage (2) include: a temperature of 600-750° C.; and a time of 1-4 hours.

23. The method according to any one of claims 1 to 4, wherein: In step 1) and step 4), the volume content of oxygen in the oxygen-containing atmosphere is 8-30%.

24. The method according to claim 23, wherein In step 1) and step 4), the volume content of oxygen in the oxygen-containing atmosphere is 10-25%.

25. The method according to any one of claims 1 to 4, wherein: In step 1) and step 4), the oxygen-containing atmosphere is a mixture of oxygen and an inert gas.

26. The method according to any one of claims 1 to 4, wherein: The waste hydrogenation catalyst is selected from at least one of a waste gasoline hydrogenation catalyst, a waste diesel hydrogenation catalyst, a waste kerosene hydrogenation catalyst and a waste wax oil hydrogenation catalyst.

27. The method according to any one of claims 1 to 4, wherein: Based on the total weight of the spent hydrogenation catalyst, the carbon content of the spent hydrogenation catalyst is less than 30%, and the deposited impurity content is less than 20%. The deposited impurity content is determined by calcining the spent hydrogenation catalyst at 600° C. in air for 3 hours and then measuring it by X-ray fluorescence spectrometry.

28. The method according to claim 27, wherein The spent hydrogenation catalyst has a carbon content of less than 15% and a deposited impurity content of less than 10%. The deposited impurity content is determined by calcining the spent hydrogenation catalyst at 600° C. in air for 3 hours and then measuring the content by X-ray fluorescence spectrometry.

29. The method according to any one of claims 1 to 4, wherein: The specific surface area of ​​the spent hydrogenation catalyst is 30-300m 2 / g, the pore volume is 0.05-0.3mL / g, and the most probable pore diameter is greater than 1nm.

30. The method according to claim 29, wherein The specific surface area of ​​the spent hydrogenation catalyst is 50-200m 2 / g, the pore volume is 0.05-0.2mL / g, and the most probable pore diameter is 1.5-4nm.

31. The method according to any one of claims 1 to 4, wherein: The spent hydrogenation catalyst includes a carrier and an active metal component supported on the carrier, wherein the active metal component includes molybdenum and / or tungsten and nickel and / or cobalt.

32. The method according to claim 31, wherein Based on the total amount of fresh catalyst corresponding to the spent hydrogenation catalyst, the content of molybdenum and / or tungsten is 10-40% by weight, and the content of nickel and / or cobalt is 1.5-8% by weight, calculated as oxides.

33. The method according to any one of claims 1 to 4, wherein: The hydrogenation protection catalyst and the hydrodemetallization catalyst each independently contain a carrier and an active metal component supported on the carrier, and the active metal component is selected from at least one metal element of Group VIB and / or Group VIII.

34. The method according to claim 33, wherein The Group VIB metal element is molybdenum and / or tungsten, and the Group VIII metal element is nickel and / or cobalt.

35. The method of claim 33, wherein: In the hydrogenation protection catalyst, the content of the active metal component is 1-15% by weight in terms of oxide, based on the total amount of the hydrogenation protection catalyst.

36. The method according to claim 35, wherein In the hydrodemetallization catalyst, the content of active metal components is 6-20% by weight, calculated as oxides, based on the total amount of the hydrodemetallization catalyst.

37. The method according to any one of claims 1 to 4, wherein: The hydrotreatment conditions include: temperature of 320-450°C, hydrogen partial pressure of 8-20 MPa, liquid hourly volume space velocity of 0.1-1 h -1 , the hydrogen to oil volume ratio is 500-1500.

38. The method of claim 37, wherein: The hydrotreatment conditions include: temperature of 350-420°C, hydrogen partial pressure of 12-18 MPa, liquid hourly volume space velocity of 0.2-0.6 h -1 , the hydrogen-to-oil volume ratio is 800-1200.

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