A method for preparing a residue hydroprocessing catalyst

Abstract

The application discloses a preparation method of a residual oil hydrogenation catalyst. The method comprises the following steps: (1) preparing a residual oil hydrogenation catalyst carrier; (2) preparing an impregnation solution containing active metals and organic oxygen-containing compounds; (3) impregnating the carrier obtained in the step (1) in the impregnation solution obtained in the step (2), and after maintenance and drying, the obtained catalyst intermediate is placed in a rotary tube furnace, is first purged with inert gas, is kept in an inert environment of a closed furnace body, is then raised to a treatment temperature, i.e. 250-850 DEG C, is treated for 2-6 hours, and a pre-carbon deposition catalyst is obtained; and (4) mixing the pre-carbon deposition catalyst obtained in the step (3) with a solution of at least one selected from potassium oleate and amine oleate, treating at 70-90 DEG C, and then drying to obtain the catalyst. The catalyst prepared by the method is particularly suitable for being used as a residual oil hydrogenation protective agent in a residual oil hydrogenation treatment process, can improve the problem of channel blockage in the late reaction stage of an existing catalyst, needs to continuously raise the temperature, and realizes long-period operation.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of residual oil hydrogenation, and particularly relates to a preparation method of a residual oil hydrogenation catalyst. BACKGROUND

[0002] With the continuous aggravation of the current trend of poor quality of crude oil, the residual oil hydrogenation treatment technology has been further concerned. It is known that a large amount of impurities in residual oil is easy to deposit on the surface of residual oil hydrogenation catalyst to block the pores of the catalysts for metal removal, which affects the treatment process of residual oil and shortens the service life of the catalyst system. Therefore, a residual oil hydrogenation catalyst with a large pore structure is usually arranged at the top of the bed to accommodate the impurities in the initial residual oil and the metal sulfide molecules obtained by metal removal, which plays an important role in the long-period operation of the residual oil hydrogenation system.

[0003] In recent years, many literatures have reported the methods for preparing residual oil hydrogenation catalysts with high specific surface area and large pore volume. The common method for obtaining a large pore structure is to mix the carrier material with a pore-expanding agent, and then to obtain a pore-expanded carrier by treating the mixture under an inert gas atmosphere for a period of time at a certain temperature. The pore-expanding agent is usually one or a mixture of active carbon, sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, etc. CN201510061806.6 discloses a preparation method of a TiO2-containing large-pore residual oil hydrogenation demetallization catalyst. The method is to mix pseudo-boehmite, sesbania powder, a pore-expanding agent, a binder and a nano-titanium hydroxide aqueous solution, to shape and calcine the mixture into a carrier, and to obtain the TiO2-containing large-pore residual oil hydrogenation demetallization catalyst by impregnating the carrier with a metal active component and then calcining. Although the catalyst prepared by adding the pore-expanding agent can improve the pore volume and has a higher accommodation capacity for the metal, sulfur and other impurities in the residual oil, the activity stability of the catalyst for long-period operation and the extension of the service life of the catalyst still need to be further improved.

[0004] CN201410284778.X discloses a preparation method of a residual oil hydrogenation catalyst, which is to use activated coal-based activated carbon and / or graphitized pore-expanding lignite carbon obtained by pore-expanding treatment as a carrier, and then to load active metal sulfide as an active component on the carrier to obtain the catalyst. Compared with the alumina carrier, the coal-based activated carbon has a problem of high impurity content, which is difficult to be made into high-performance activated carbon, and thus is difficult to be applied to harsh environments. On the other hand, the pore-expanding activated carbon carrier generally has the problem of low mechanical strength and fast abrasion, and the replacement cost is relatively high. Meanwhile, with the rise of the price of coal, the price advantage of the coal-based activated carbon is gradually lost.

[0005] A big difficulty in the residue hydrogenation reaction is coking. Due to the presence of acid centers, coke will gradually form on the surface of the catalyst. The coke will make the catalyst activity decrease, because the carbon compounds are strongly adsorbed on the acid centers, covering the active centers, and due to the accumulation of coke, the pores are blocked, so that the reactants cannot approach the active centers to be adsorbed, greatly reducing the surface utilization of the catalyst. At the beginning of the reaction, the amount of carbon begins to increase rapidly, and the catalyst activity also decreases rapidly. The pre-coke catalyst can be passivated by pre-coke of the catalyst, which actually slightly reduces the initial activity of the catalyst, and improves the selectivity and stability of the catalyst. Although the pre-coke catalyst for residue hydrogenation can achieve long-period operation of the reaction to a certain extent, it is inevitable that at the later stage of the reaction, due to too much coke blocking the pores of the catalyst, the activity decreases too much, and the temperature needs to be increased to compensate. SUMMARY

[0006] In view of the deficiencies of the prior art, the present application provides a preparation method of a residue hydrogenation catalyst. The catalyst prepared by the method of the present application is particularly suitable as a residue hydrogenation protective agent for use in the residue hydrogenation treatment process, which can improve the problem of pore blockage of the existing catalyst at the later stage of the reaction, and the need for continuous temperature increase, and achieve long-period operation

[0007] The present application provides a preparation method of a residue hydrogenation catalyst, which comprises:

[0008] (1) preparing a residue hydrogenation catalyst carrier;

[0009] (2) preparing an impregnation solution containing active metals and organic oxygen-containing compounds;

[0010] (3) impregnating the carrier obtained in step (1) in the impregnation solution obtained in step (2), and after aging and drying, the obtained catalyst intermediate is placed in a rotary tube furnace, first purged with inert gas to maintain an inert environment in the furnace body, then the furnace temperature is raised to a treatment temperature of 250-850℃, and treated for 2-6 hours to obtain a pre-coke catalyst;

[0011] (4) mixing the pre-coke catalyst obtained in step (3) with a solution of at least one selected from potassium oleate and amine oleate, treating at 70-90℃, and then drying to obtain the catalyst.

[0012] In the present application, in step (1), the residue hydrogenation catalyst carrier can be prepared by conventional methods, such as: mixing the residue hydrogenation catalyst carrier material, pore expanding agent and binder, shaping, drying and calcining to obtain the carrier.

[0013] In the present application, the residue hydro-treating catalyst carrier material in step (1) can be a conventional residue hydro-treating catalyst carrier material, such as an alumina-based carrier material. Generally, the carrier material is an un-calcined carrier material, such as aluminum hydroxide, or an aluminum hydroxide containing conventional adjuvants. The conventional adjuvants can be selected from at least one of silicon, boron, phosphorus, magnesium, etc., and the content of the adjuvants is less than 15% of the dry mass of the carrier material. Preferably, the carrier material has the following properties: specific surface area of 100-180 m 2 / g, pore volume of 0.3-0.5 mL / g.

[0014] In the present application, the pore-expanding agent in step (1) is preferably a fiber with a length of 1-2 mm and a diameter of 30-50 μm. The amount of the pore-expanding agent added is 2%-4% of the dry mass of the carrier material.

[0015] In the present application, the binder in step (1) can be a conventional binder, and preferably is methyl cellulose. The amount of the binder added is 2%-30% of the dry mass of the carrier material.

[0016] In the present application, the molding in step (1) can be performed by a conventional molding method, and preferably is extrusion molding. A conventional molding adjuvant, such as an extrusion aid, can be added during the molding process, and the extrusion aid is selected from pearl millet powder.

[0017] In the present application, the drying conditions in step (1) are as follows: temperature of 50-120°C, and time of 1-10 hours.

[0018] In the present application, the calcination conditions in step (1) are as follows: temperature of 400-700°C, and time of 1-6 hours.

[0019] In the present application, the pore distribution of the carrier in step (1) is as follows: the pore volume of the pores with a pore diameter less than 10 nm is less than 10% of the total pore volume, the pore volume of the pores with a pore diameter of 10-35 nm is 45%-70% of the total pore volume, the pore volume of the pores with a pore diameter of 35-50 nm is 10%-30% of the total pore volume, and the pore volume of the pores with a pore diameter greater than 50 nm is 5%-10% of the total pore volume.

[0020] In the present application, the active metal in step (2) is selected from at least one of a Group VIB metal and a Group VIII metal, wherein the Group VIB metal is preferably Mo and / or W, and the Group VIII metal is preferably Co and / or Ni.

[0021] In the present application, the concentration of the Group VIB metal in the impregnation solution of step (2) is 2.5%-7.5% as oxide, the concentration of the Group VIII metal is 0.5%-2.5% as oxide, and optionally, the concentration of the phosphorus source is 2.5%-4.0% as P. The active metal precursor can be a conventional material, for example, the molybdenum precursor can be at least one of ammonium molybdate and molybdenum trioxide, the tungsten precursor can be a tungstate, the cobalt precursor can be cobalt nitrate, and the nickel precursor can be at least one of nickel nitrate and basic nickel carbonate. The phosphorus source can be phosphoric acid.

[0022] In the present application, the organic oxygen-containing compound in step (2) is preferably at least one of an organic alcohol and an organic ether, and the carbon number of the organic oxygen-containing compound is 1-3. The organic oxygen-containing compound is preferably at least one of methanol and dimethyl ether. The mass concentration of the organic oxygen-containing compound in the impregnation solution is 10%-30%.

[0023] In the present application, the preparation temperature of the impregnation solution in step (2) is 50-85°C, and the pH value is 3-6, which can be adjusted by at least one of citric acid and acetic acid.

[0024] In the present application, the impregnation in step (3) is preferably saturated impregnation.

[0025] In the present application, in step (3), the furnace temperature is preferably raised to the first treatment temperature, i.e. 300-480°C, for 1-3 hours, and then the furnace temperature is raised to the second treatment temperature, i.e. 800-850°C, for 1-3 hours.

[0026] In the present application, the initial temperature of the rotary tube furnace is 10°C-30°C, the temperature rising rate is 3-5°C / min, and the temperature is raised to the treatment temperature. The treatment atmosphere is a water vapor atmosphere, and the volume ratio of the catalyst intermediate to the water vapor volume in the furnace body is 1:(35-50).

[0027] In the present application, in step (3), the pre-coke catalyst preferably has a coke content of 1%-3% by mass.

[0028] In the present application, in step (3), the curing conditions are as follows: the temperature is 15-35°C, and the time is 8-15 hours.

[0029] In the present application, in step (3), the drying conditions are as follows: the temperature is 100-200°C, and the time is 4-8 hours.

[0030] In the present application, in step (3), the inert gas can be nitrogen.

[0031] In the present application, in step (4), the solid-liquid volume ratio of the pre-coke catalyst obtained in step (3) to the solution selected from at least one of potassium oleate and amine oleate is 1:1-3.

[0032] In the present application, the mass concentration of the solution of at least one selected from potassium oleate and amine oleate in step (4) is 15%-20%.

[0033] In the present application, the pre-carbonized catalyst obtained in step (3) is mixed with a solution of at least one selected from potassium oleate and amine oleate in step (4), and preferably treated at 70-90℃ for 0.5-1.0h.

[0034] In the present application, the drying conditions in step (4) are as follows: drying at 50-200℃ for 4-8h to obtain the catalyst.

[0035] The present application also provides the hydrogenation catalyst prepared by the above method.

[0036] In the present application, the shape of the catalyst particles is preferably four-blade type, and the particle size is 2-4mm.

[0037] In the present application, the carbon deposition amount of the catalyst is 0.3%-1.5% by mass.

[0038] In the present application, preferably, the carbon deposition amount of the catalyst is at least 0.2 percentage points lower than that of the pre-carbonized catalyst, and preferably at least 0.8 percentage points lower.

[0039] In the present application, the content of the Group VIB metal in the catalyst is 2.5%-7.5% as oxide based on the mass of the catalyst, and the content of the Group VIII metal is 0.5%-2.5% as oxide.

[0040] In the present application, the catalyst is preferably a residual oil hydrogenation guard.

[0041] Compared with the prior art, the preparation method of the catalyst of the present application has the following advantages:

[0042] In the preparation method of the catalyst of the present application, a catalyst carrier with a specific pore distribution is first prepared, and then a rotary furnace is used to treat the catalyst intermediate to form carbon deposition on the surface and in the pores of the catalyst under high temperature conditions. Then, the pre-carbonized catalyst is treated with a solution of at least one selected from potassium oleate and amine oleate, so that more carbon deposition sites are retained on the inner surface of the catalyst pores, and part of the carbon deposition on the outer surface of the catalyst is removed, so that the carbon deposition content increases from the outside to the inside. In the early stage of the reaction, the outer surface has relatively less carbon deposition and relatively higher activity, while the inner surface has relatively more carbon deposition and relatively lower activity, so that the carbon deposition formed during the reaction is first formed on the outer surface, and the internal pores remain unobstructed. In the later stage of the reaction, the activity of the outer surface of the catalyst decreases sharply, but due to the existence of the mechanical pores, the reaction can still proceed at a certain rate on the inner surface to continue the reaction, which is beneficial to the long-period operation of the catalyst.

[0043] The catalyst prepared by the method of the present application is particularly suitable as a residue hydroprocessing guard for use in a residue hydroprocessing process, and can improve the problem of channel blockage in the later reaction stage of the existing catalyst, and can realize long-period operation. DETAILED DESCRIPTION

[0044] The technical solutions of the present application are further described below in combination with specific examples, but the protection scope of the present application is not limited by the examples.

[0045] In the present application, the specific surface area, pore volume and pore distribution are characterized by BET, and the instrument is BSD-PS specific surface area and pore size analyzer. The output pressure is 0.15±0.02 MPa during testing; the sample weight is 20-100 mg 2 , and the upper limit of the sample weight is not more than 2 / 3 of the ball part of the sample tube, and the lower limit is not less than 100 mg.

[0046] Example 1

[0047] Select 145 g of alumina powder, add 3 g of fiber (length 1-2 mm, diameter 30-50 μm), 3 g of sesbania powder, 3 g of cellulose, 3 g of boric acid, 180 g of water, mix uniformly, knead, extrude 4 mm hole plate four impeller, dry at 120℃ for 5 hours, calcine at 600℃ for 3 hours, and prepare the carrier. The properties of the carrier material are as follows: the specific surface area is 141 m 2 / g, the pore volume is 0.43 mL / g, and the pore distribution is as follows: the pore volume of the pores with a pore diameter of 10 nm or less accounts for 8% of the total pore volume, the pore volume of the pores with a pore diameter of 10-35 nm accounts for 60% of the total pore volume, the pore volume of the pores with a pore diameter of 35-50 nm accounts for 24% of the total pore volume, and the pore volume of the pores with a pore diameter greater than 50 nm accounts for 8% of the total pore volume.

[0048] An impregnation solution containing active metals is prepared, using water as the solvent, 6.7 wt% of MoO3, 1.4 wt% of NiO, and 3.2% of P (calculated as P) of phosphoric acid (concentration 85 wt%) are mixed at 50℃ to prepare the impregnation solution, and the pH value is 5. In the impregnation solution, 12% of dimethyl ether is added by mass concentration.

[0049] The carrier is saturatedly impregnated with the impregnation solution, and after 8 hours of incubation at 25℃ and 3 hours of drying at 120℃, a catalyst intermediate is obtained, which is placed in a rotary furnace. First, it is purged with inert gas, and then water vapor is introduced at a volume ratio of the catalyst intermediate to the water vapor in the furnace body of 1:40, the furnace temperature is increased to 475℃ at a rate of 200℃ per hour, heated for 1.5 hours, and then increased to 840℃ for 1.2 hours to obtain a pre-carbon deposition catalyst. The carbon deposition amount of the pre-carbon deposition catalyst is 2.4%.

[0050] The pre-coke catalyst was cooled to room temperature. A potassium oleate solution (mass concentration 17%) was heated to 80°C, and the pre-coke catalyst was impregnated with the solution at a solid-liquid volume ratio of 1:1.5 for 0.5 h, and then dried at 200°C for 6 h to obtain catalyst C1.

[0051] The coke content of the obtained catalyst was 1.3% by mass.

[0052] The MoO3 content of the obtained catalyst was 2.7% by mass, and the NiO content was 0.8% by mass.

[0053] Example 2

[0054] A 145 g of alumina powder, 4.5 g of fibers (length 1-2 mm, diameter 30-50 μm), 5 g of sesbania powder, 4 g of methyl cellulose, 3 g of boric acid, and 200 g of water were mixed uniformly, and then kneaded and extruded through a 4 mm orifice plate four-blade impeller. The extrudate was dried at 120°C for 5 h and calcined at 650°C for 3 h to obtain a carrier. The properties of the carrier material were as follows: specific surface area 150 m 2 / g, pore volume 0.45 mL / g, and pore distribution as follows: pore volume of pores with a pore diameter of 10 nm or less was 6% of the total pore volume, pore volume of pores with a pore diameter of 10-35 nm was 59% of the total pore volume, pore volume of pores with a pore diameter of 35-50 nm was 28% of the total pore volume, and pore volume of pores with a pore diameter of more than 50 nm was 7% of the total pore volume.

[0055] An impregnation solution containing active metals was prepared using water as a solvent, 6.0 wt% MoO3, 1.2 wt% NiO, and 3.1% P (as H3PO4, concentration 85 wt%) mixed at 50°C, and the pH was adjusted to 6. Methanol was added to the impregnation solution at a mass concentration of 28%.

[0056] The carrier was saturated impregnated with the impregnation solution, and then incubated at 25°C for 8 h and dried at 120°C for 3 h to obtain a catalyst intermediate. The catalyst intermediate was placed in a rotary furnace, and then saturated with inert gas. Water vapor was introduced at a volume ratio of the catalyst intermediate to water vapor of 1:45, and the furnace temperature was increased to 405°C at a rate of 200°C / hour, and then heated for 2.0 h. The temperature was further increased to 810°C, and the catalyst was treated at this temperature for 2.0 h to obtain a pre-coke catalyst. The coke content of the pre-coke catalyst was 2.3%.

[0057] The pre-coke catalyst was cooled to room temperature. An amine oleate solution (mass concentration 19%) was heated to 80°C, and the pre-coke catalyst was impregnated with the solution at a solid-liquid volume ratio of 1:1.5 for 0.5 h, and then dried at 200°C for 6 h to obtain catalyst C2.

[0058] The carbon deposition amount of the obtained catalyst was 1.2% by mass.

[0059] The mass content of MoO3 in the obtained catalyst was 2.5%, and the mass content of NiO was 0.7%.

[0060] Example 3

[0061] The carrier and the impregnation solution were the same as in Example 1.

[0062] The carrier was saturatedly impregnated with the impregnation solution, and after aging at 25°C for 8 hours and drying at 120°C for 3 hours, a catalyst intermediate was obtained and placed in a rotary furnace. The furnace was first purged with inert gas, and then water vapor was introduced at a volume ratio of the catalyst intermediate to water vapor of 1:35, and the furnace temperature was raised to 475°C at a rate of 200°C per hour, and heated for 2.5 hours, and then raised to 840°C for 2.8 hours to obtain a pre-carbon deposition catalyst. The carbon deposition amount of the pre-carbon deposition catalyst was 2.7%.

[0063] The pre-carbon deposition catalyst was allowed to cool to room temperature. An amine oleate solution (mass concentration 19%) was heated to 80°C, and the pre-carbon deposition catalyst was impregnated with the potassium oleate solution at a solid-liquid volume ratio of 1:2.0 for 0.5 hours and dried at 200°C for 6 hours to obtain catalyst C3.

[0064] The carbon deposition amount of the obtained catalyst was 1.5% by mass.

[0065] The mass content of MoO3 in the obtained catalyst was 2.8%, and the mass content of NiO was 0.9%.

[0066] Comparative Example 1

[0067] The pre-carbon deposition catalyst was used as catalyst DC1 compared with Example 1.

[0068] 145 g of alumina powder, 3 g of fiber (length 1-2 mm, diameter 30-50 μm), 3 g of sesbania powder, 3 g of cellulose, 3 g of boric acid, and 180 g of water were mixed uniformly, and then kneaded, extruded through a 4 mm hole plate four-blade impeller, dried at 120°C for 5 hours, and calcined at 600°C for 3 hours to obtain a carrier. The properties of the carrier material were as follows: specific surface area 141 m 2 / g, pore volume 0.43 mL / g, and pore distribution as follows: pore volume of pores with pore diameter of 10 nm or less was 8% of the total pore volume, pore volume of pores with pore diameter of 10-35 nm was 60% of the total pore volume, pore volume of pores with pore diameter of 35-50 nm was 24% of the total pore volume, and pore volume of pores with pore diameter of greater than 50 nm was 8% of the total pore volume.

[0069] An impregnation solution containing active metals is prepared using water as solvent, 6.7 wt% of molybdenum trioxide as MoO3, 1.4 wt% of basic nickel carbonate as NiO, and 3.2% of phosphoric acid (concentration 85 wt%) as P, mixed at 50°C, and pH 5. Dimethyl ether is added to the impregnation solution at a mass concentration of 12%. The carrier is saturated impregnated with the impregnation solution, and then incubated at 25°C for 8 hours and dried at 120°C for 3 hours to obtain a catalyst intermediate, which is placed in a rotary furnace. The furnace is first purged with inert gas, and then water vapor is introduced at a volume ratio of the catalyst intermediate to water vapor in the furnace of 1:40. The furnace temperature is increased to 475°C at a rate of 200°C per hour, heated for 1.5 hours, and then increased to 840°C for 1.2 hours to obtain a pre-coke catalyst DC1. The coke content of the pre-coke catalyst is 2.4%.

[0070] Comparative Example 2

[0071] The carrier is the same as in Example 1.

[0072] An impregnation solution containing active metals is prepared using water as solvent, 6.7 wt% of molybdenum trioxide as MoO3, 1.4 wt% of basic nickel carbonate as NiO, and 3.2% of phosphoric acid (concentration 85 wt%) as P, mixed at 50°C, and pH 5. Methanol is added to the impregnation solution at a mass concentration of 7%.

[0073] The carrier is saturated impregnated with the impregnation solution, and then incubated at 25°C for 8 hours and dried at 120°C for 3 hours to obtain a catalyst intermediate, which is placed in a rotary furnace. The furnace is first purged with inert gas, and then water vapor is introduced at a volume ratio of the catalyst intermediate to water vapor in the furnace of 1:40. The furnace temperature is increased to 475°C at a rate of 200°C per hour, heated for 1.0 hour, and then increased to 840°C for 1.0 hour to obtain a pre-coke catalyst DC2.

[0074] The coke content of the obtained catalyst is 1.3% by mass.

[0075] In the obtained catalyst, the mass content of MoO3 is 2.7%, and the mass content of NiO is 0.8%.

[0076] Application Example

[0077] The present example gives a catalyst grading scheme for long period operation of raw material, the catalysts C1, C2 and C3 of the present application and the comparative examples DC1 and DC2 and the conventional hydrogenation guard FZC-100B are respectively loaded into a fixed bed hydrogenation reactor as guard, and then the bed is loaded from top to bottom with a hydrogenation demetallization catalyst (FZC-204A), a hydrogenation desulfurization catalyst (FZC-33B) and a hydrogenation denitrification catalyst (FZC-41B) in a volume ratio of 10%:40%:25%:25%. Before reaction, the catalysts need to be sulfided first, the process is as follows: heating to 350°C at 10°C / h, injecting dimethyl disulfide (DMDS) vacuum gas oil (VGO) into the device at a volume space velocity of 0.30h -1 -1. The reaction pressure is 15.7 MPa, the hydrogen oil volume ratio is 758, and the sulfidation time is 40 h. The treated raw material (see Table 1), the test conditions are as follows: reaction temperature 385°C, hydrogen oil volume ratio 1000, liquid hourly space velocity 1.0h -1 -1, hydrogen partial pressure 14 MPa, continuous operation time and corresponding oil impurity removal effect are shown in Table 2.

[0078] Table 1 Raw material oil properties

[0079]

[0080]

[0081] Table 2 Evaluation results of catalysts in each example

[0082]

[0083] From the results in Table 2, it can be seen that the catalysts of the present application have higher stability and are suitable for long period operation.

Claims

1. A method for preparing a residue oil hydrotreating catalyst, comprising: (1) Preparation of a catalyst support for residue oil hydrogenation; (2) Prepare an impregnation solution containing active metals and organic oxygen-containing compounds; (3) The carrier obtained in step (1) is impregnated in the impregnation liquid obtained in step (2). After curing and drying, the resulting catalyst intermediate is placed in a rotary tube furnace. First, it is purged with inert gas to maintain a sealed inert environment in the furnace body. Then, the furnace temperature is raised to the processing temperature to obtain a pre-coated catalyst. (4) The pre-coking catalyst obtained in step (3) is mixed with a solution selected from at least one of potassium oleate and amine oleate, treated at 70-90°C, and then dried to obtain the catalyst; The catalyst support for residue hydrotreating mentioned in step (1) is an alumina-based support; the pore distribution of the support is as follows: pores with a diameter less than 10 nm occupy less than 10% of the total pore volume, pores with a diameter of 10-35 nm occupy 45%-70% of the total pore volume, pores with a diameter of 35-50 nm occupy 10%-30% of the total pore volume, and pores with a diameter greater than 50 nm occupy 5%-10% of the total pore volume; The active metal in step (2) is selected from at least one of Group VIB metals and Group VIII metals, wherein the Group VIB metal is Mo and / or W, and the Group VIII metal is Co and / or Ni; In step (2), the concentration of Group VIB metals as oxides in the impregnation solution is 2.5%-7.5%, and the concentration of Group VIII metals as oxides is 0.5%-2.5%. The organic oxygen-containing compound mentioned in step (2) is at least one of organic alcohol and organic ether, and the organic oxygen-containing compound has 1-3 carbon atoms; In step (3), the furnace temperature is raised to the first processing temperature of 300-480℃ for 1-3 hours, and then the furnace temperature is raised to the second processing temperature of 800-850℃ for 1-3 hours. The processing atmosphere in step (3) is a water vapor atmosphere, wherein the volume ratio of the catalyst intermediate to the water vapor volume in the furnace is 1:(35-50). In step (3), the carbon deposition amount of the pre-coated catalyst is 1%-3% by mass; In step (4), the mass concentration of the solution selected from at least one of potassium oleate and amine oleate is 15%-20%; the solid-liquid volume ratio of the pre-coated catalyst obtained in step (3) to the solution selected from at least one of potassium oleate and amine oleate is 1:1-3.

2. The preparation method according to claim 1, characterized in that, In step (1), the carrier has the following properties: specific surface area of ​​100-180 m². 2 / g, with a pore volume of 0.3-0.5mL / g.

3. The preparation method according to claim 1, characterized in that, In step (2), a phosphorus source is added to the impregnation solution. The concentration of the phosphorus source, calculated as P, is 2.5%-4.0%.

4. The preparation method according to claim 1, characterized in that, In step (2), the organic oxygen-containing compound is at least one of methanol and dimethyl ether; and / or, the mass concentration of the organic oxygen-containing compound in the impregnation solution is 10%-30%.

5. The preparation method according to claim 1, characterized in that, The impregnation solution in step (2) is prepared at a temperature of 50-85℃ and a pH value of 3-6.

6. The preparation method according to claim 1, characterized in that, The impregnation in step (3) is saturated impregnation; and / or, the drying conditions in step (3) are as follows: temperature is 100-200℃, time is 4-8 hours, and the curing conditions are as follows: temperature is 15-35℃, time is 8-15 hours.

7. The preparation method according to claim 1, characterized in that, In step (4), the amount of carbon deposited in the catalyst is 0.3%-1.5% by mass.

8. The preparation method according to claim 7, characterized in that, The amount of carbon deposited in the catalyst is at least 0.2 percentage points lower than that in the pre-coated catalyst.

9. The preparation method according to claim 8, characterized in that, The amount of carbon deposited in the catalyst is at least 0.8 percentage points lower than that in the pre-coated catalyst.

10. The preparation method according to claim 1, characterized in that, The drying conditions in step (4) are as follows: dry at 50-200℃ for 4-8 hours to obtain the catalyst.

11. The residue hydrotreating catalyst prepared by any one of claims 1-10.

12. The catalyst according to claim 11, characterized in that, The catalyst is a residual oil hydrotreating protectant.

13. The catalyst according to claim 12, characterized in that, Based on catalyst mass, the content of Group VIB metals as oxides is 2.5%-7.5%, and the content of Group VIII metals as oxides is 0.5%-2.5%.

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