A hydroprocessing catalyst and a method for making the same

Abstract

The application discloses a kind of hydroprocessing catalyst and its preparation method.The hydroprocessing catalyst includes the alumina carrier of core-shell structure, hydrogenation active metal;The shell layer is in situ grown in core phase, and the shell layer is sheet-like alumina crystal aggregate, and the core phase is worm-like alumina crystal aggregate.Preparation method is as follows: (1) using hydrogenation active metal solution to impregnate pseudo-boehmite, then powder and propylene oxide aqueous solution are mixed to hydrothermal treatment, and ball is formed, to obtain alumina carrier precursor;(2) the alumina carrier precursor obtained is mixed with propylene oxide aqueous solution to carry out hydrothermal treatment, and hydrogenation active metal is loaded, to obtain catalyst.The catalyst pore structure is gradient distribution, and has higher hydrogenation demetallization, desulfurization, denitrification, de-carbon activity in the process of distillate oil hydroprocessing.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalyst preparation, and particularly relates to a hydroprocessing catalyst and a preparation method thereof. BACKGROUND

[0002] With the heavy and poor quality of crude oil and the increasing demand for high-quality light fuel oil, the processing technology of poor heavy oil has become the research focus of major oil companies and petroleum research institutions. Among them, the hydroprocessing technology is one of the most effective technical solutions to improve the quality of poor heavy oil and provide high-quality raw oil for downstream devices, and is currently widely concerned.

[0003] The residual oil hydrogenation technology generally adopts grading technology, and the commonly used catalyst grading includes the collocation of four catalysts. The first stage is a protective agent for removing iron, calcium, sodium and other easily removable impurities in residual oil. The catalyst is characterized by high carrier porosity and low active metal content. The second stage is a metal removal catalyst for removing metal nickel, metal vanadium and other impurities in residual oil. The carrier of the catalyst is generally a large-pore carrier with bimodal pore distribution, and the active metal loading is 5%-12%. The third stage is a desulfurization catalyst, and the carrier has smaller pore size and stronger acidity than the metal catalyst carrier. The metal loading reaches 8%-15%. The fourth stage is mainly a denitrification catalyst for hydrodenitrogenation, which has the strongest acidity and the highest metal loading of 12%-25%.

[0004] CN113042064A discloses a preparation method of a residual oil hydroprocessing catalyst carrier and a catalyst. The preparation method of the catalyst comprises: treating an alumina-based carrier intermediate with a solution containing a porphyrin copper and / or zinc compound, drying and calcining to obtain a residual oil hydroprocessing catalyst carrier, and impregnating the carrier prepared by the above method with an active metal component, drying and calcining to obtain a residual oil hydroprocessing catalyst. The catalyst prepared by the method is used in the residual oil hydrodemetallization process, and the metal impurities such as vanadium in the raw material can easily diffuse into the internal pores of the catalyst for reaction and deposition, thereby greatly reducing the deposition amount of vanadium and other impurities at the catalyst orifice, avoiding orifice blockage, enhancing the catalyst's ability to remove impurities, avoiding rapid rise of the catalyst bed pressure drop, and being conducive to prolonging the service life of the catalyst.

[0005] CN110841651A discloses a boron-containing residual oil hydroprocessing catalyst and a preparation method thereof. The catalyst preparation steps are as follows: (1) preparing an aluminum salt solution, mixing the sol by using a pH swing method, adding an organic pore-expanding agent solution containing a titanium compound in the mixing process, leading into a gelatinizing tank, and gelatinizing at 60-90 DEG C. After gelatinizing, aging, drying, and molding, the catalyst is calcined at 550-1100 DEG C to obtain an alumina carrier; (2) immersing the alumina carrier in an impregnation solution of Mo or W and Co or Ni, drying at 90-150 DEG C for 2-8 hours, and calcining at 600-800 DEG C for 1-5 hours to obtain a hydrodemetallization catalyst.

[0006] The pore gradient of the hydroprocessing catalyst prepared by the prior art is poor, which is not conducive to the effective diffusion of reactants of different sizes and the full play of the pore performance of the catalyst, and it is difficult to make the catalyst have high hydrodemetallization, desulfurization, denitrification and de-carbon activity at the same time. SUMMARY

[0007] In view of the deficiencies in the prior art, the present application provides a hydroprocessing catalyst and a preparation method thereof. The catalyst has a gradient pore structure and high hydrodemetallization, desulfurization, denitrification and de-carbon activity during distillate oil hydroprocessing.

[0008] The hydroprocessing catalyst of the present application comprises an alumina carrier with a core-shell structure, a first hydroactive metal and a second hydroactive metal; the shell layer is in situ grown on the core phase, the shell layer is a flaky alumina grain aggregate, and the core phase is a vermicular alumina grain aggregate; the thickness of the shell layer is 0.3-1.5 μm, and the diameter of the core phase is 1-5 mm; the first hydroactive metal is Mo and / or W, and the second hydroactive metal is Ni and / or Co.

[0009] The size of the flaky alumina grain is 100-600 nm, and the size of the vermicular alumina grain is 80-260 nm.

[0010] The specific surface area of the hydroprocessing catalyst of the present application is 200-300 m 2 / g, the pore volume is 0.75-1.0 mL / g, and the 8-15 nm pore accounts for 55%-70% of the total pore volume.

[0011] The preparation method of the hydroprocessing catalyst of the present application comprises the following contents:

[0012] (1) impregnate pseudo-boehmite with a solution containing first and second hydrogenation active metals, dry and calcine the impregnated material to obtain active metal modified gamma phase alumina powder, then mix the powder with propylene oxide aqueous solution, and then perform hydrothermal treatment, filter, wash and dry the treated material to obtain worm-like particles R1, then roll ball form and calcine to obtain an alumina carrier precursor;

[0013] (2) mix the obtained alumina carrier precursor with propylene oxide aqueous solution, then perform hydrothermal treatment, filter, wash and dry the treated material, and then load first and second hydrogenation active metals to obtain a hydroprocessing catalyst.

[0014] In the method of the present application, the first hydrogenation active metal in step (1) is Mo and / or W, and the second hydrogenation active metal is Ni and / or Co; the solution containing the first and second hydrogenation active metals is prepared according to the methods well known to those skilled in the art, wherein the content of the first hydrogenation active metal in the solution is 11.5-15.5 g / 100 mL as calculated based on the oxide, the content of the second hydrogenation active metal in the solution is 2.9-3.9 g / 100 mL as calculated based on the oxide, and the amount of the solution used is the saturated water absorption of the pseudo-boehmite.

[0015] In the method of the present application, the drying and calcining in step (1) are performed under the following conditions: the drying temperature is 100-160°C, and the drying time is 3-8 hours; the calcining temperature is 400-650°C, and the calcining time is 4-8 hours.

[0016] In the method of the present application, the concentration of the propylene oxide aqueous solution in step (1) is 2.5wt%-12wt%, preferably 4wt%-8wt%, and the mass ratio of the amount of the propylene oxide aqueous solution to the active metal modified gamma phase alumina powder is 3:1-10:1, preferably 4:1-8:1. The sealing heat treatment is preferably performed in an autoclave, and the heat treatment temperature is 110-180°C, preferably 120-160°C, and the heat treatment time is 1-3 hours.

[0017] In the method of the present application, the gamma phase alumina powder in step (1) can be commercially available, or can be prepared according to the prior art. Generally, commercially available or self-prepared pseudo-boehmite precursors according to the prior art are used as raw materials, and are calcined to obtain the gamma phase alumina powder; the calcining temperature is 400-600°C, and the calcining time is 4-8 hours.

[0018] In the method, the step (1) is carried out in a rotary table forming machine, and the rotary table forming machine is operated under the conditions that the inclination angle of the rotary table is 40-70° and the rotary speed of the rotary table is 10-30 rpm; the forming time of the material in the rotary table is 10-120 min. A water solution containing a glue solvent is sprayed into the material during the rolling ball forming process; the water solution containing the glue solvent is one or a mixture of several of the water solutions of nitric acid, phosphoric acid, oxalic acid, acetic acid and boric acid, and the mass concentration of the solution is 1-3%, preferably the water solution of boric acid.

[0019] In the method, the concentration of the propylene oxide water solution in the step (2) is 2.5wt%-12wt%, preferably 4wt%-8wt%, and the mass ratio of the propylene oxide water solution to the alumina carrier precursor is 3:1-10:1, preferably 4:1-8:1. The sealing heat treatment is carried out in a sealed container, preferably an autoclave, the sealing heat treatment temperature is 110-180℃, preferably 120-160℃, the hydrothermal treatment time is 14-20 hours, the drying temperature is 100-160℃, and the drying time is 4-10 hours; the calcination temperature is 450-550℃, and the calcination time is 4-8 hours.

[0020] In the method, the first hydrogenation active metal in the step (2) is Mo and / or W, and the second hydrogenation active metal is Ni and / or Co; the loading is carried out by an equal-volume impregnation method, and the solution containing the first and second hydrogenation active metals is prepared according to the method known to those skilled in the art, in which the content of the first hydrogenation active metal in the solution is 8.5-12.5g / 100mL in terms of oxide, and the content of the second hydrogenation active metal is 2.2-3.1g / 100mL in terms of oxide; the impregnated material is dried and calcined to obtain a hydrogenation treatment catalyst, in which the drying temperature is 100-160℃, and the drying time is 3-8 hours. The calcination temperature is 450-550℃, and the calcination time is 4-8 hours.

[0021] Compared with the prior art, the method has the following advantages:

[0022] This invention first prepares worm-like pseudoboehmite modified with active metal, which is obtained by heat-treating active metal-modified γ-phase alumina powder in a propylene oxide solution. The pseudoboehmite particles prepared in this process have a worm-like morphology, and the loosely packed worm-like particles increase the content of 8-15 nm pores in the catalyst. On the other hand, the modified active metal component coordinates the rehydration process of the γ-phase alumina, effectively regulating the interaction between the active metal and the support. During support formation, the worm-like particles serve as the "core phase" raw material for the alumina support, and the "core phase" has numerous 8-15 nm pores. During the secondary hydrothermal treatment, the in-situ grown lamellar particles serve as the "shell layer" of the alumina support, and the lamellar alumina grains aggregate to form numerous 40-300 nm pores. Finally, the alumina support pores exhibit a gradient distribution, meaning the "shell layer" pores are larger and more interconnected, while the "core phase" pores are smaller and more concentrated. This pore structure facilitates the hydrotreating of heavy residue oil, where the "core phase" undergoes hydrodemetallization and desulfurization reactions first, followed by further diffusion of the reactants into the "core phase" for hydrodesulfurization, denitrification, and decarbonization. The large, well-connected pores in the support "shell" provide strong resistance to metal deposition and carbon buildup. The active metal component in the catalyst is introduced in two steps: firstly, it reduces the difficulty of preparing high-concentration active component impregnation solutions and the erosion of the support pores by high-concentration Mo-Ni-P solutions; secondly, it effectively regulates the interaction between the active metal and the support, thereby improving the catalyst's hydrotreating activity. Attached Figure Description

[0023] Figure 1 This is a SEM image of the worm-like pseudoboehmite prepared in Example 1.

[0024] Figure 2 This is a SEM image of the outer surface of the alumina carrier prepared in Example 1. Detailed Implementation

[0025] The technical solution and effects of the present invention will be further illustrated below with reference to the embodiments, but the invention is not limited to the following embodiments. In the present invention, wt% represents mass fraction.

[0026] BET Method: The pore structure of the carriers in the examples and comparative examples was characterized using N2 physical adsorption-desorption. The specific procedure was as follows: The pore structure of the samples was characterized using an ASAP-2420 N2 physical adsorption-desorption instrument. A small amount of sample was vacuum-treated at 300℃ for 3-4 hours, and finally, the product was placed under liquid nitrogen cryogenic conditions (-200℃) for nitrogen adsorption-desorption testing. The specific surface area was obtained according to the BET equation, and the pore volume and pore diameter distribution below 30nm were obtained according to the BJH model.

[0027] The microstructure of the alumina support was characterized using scanning electron microscopy. The specific operation was as follows: The microstructure of the support was characterized using a JSM-7500F scanning electron microscope with an accelerating voltage of 5KV, an accelerating current of 20µA, and a working distance of 8mm. Example 1

[0028] (1) Weigh 500g of pseudoboehmite powder, impregnate the pseudoboehmite with a Mo-Ni-P solution containing 12.5g / 100mL of MoO3 and 3.1g / 100mL of NiO, and dry the impregnated material at 120℃ for 6 hours and calcine at 450℃ for 5 hours to obtain active metal modified γ phase alumina powder.

[0029] Weigh 100 g of the above-mentioned active metal-modified γ-phase alumina powder, add 650 g of a 5.5% (w / w) propylene oxide aqueous solution, stir magnetically for 30 minutes, then transfer the mixture to an autoclave, seal it, and heat it at 150°C for 1.8 hours. After cooling, filter and wash the solid material, and dry it at 120°C for 6 hours to obtain powder material R1-1. The scanning electron microscope image is shown below. Figure 1 .

[0030] (2) Place the powder material R1-1 from step (1) into the rotary molding machine, adjust the tilt angle of the rotary table to 50º, and the rotation speed of the rotary table to 20rpm. Spray a 1.5% boric acid aqueous solution onto the material in the rotary table through a sprayer. After mixing and contact, the material is formed in the rotary table for 45 minutes to obtain the alumina carrier precursor.

[0031] (3) Weigh 100 g of the alumina carrier precursor from step (2) and add 6.7% cyclohexane.

[0032] 620 g of oxypropane aqueous solution was magnetically stirred for 30 minutes, then the mixture was transferred to an autoclave, sealed, and heated at 145°C for 18 hours. After cooling, the solid material was filtered, dried at 120°C for 6 hours, and calcined at 450°C for 5 hours to obtain an alumina support. A scanning electron microscope image of the outer surface of the support is shown below. Figure 2 .

[0033] (4) Weigh 50 g of the alumina support from step (3), and impregnate the support with an equal volume of Mo-Ni-P solution containing 11.0 g / 100 mL of MoO3 and 2.8 g / 100 mL of NiO. After impregnation, the material is dried at 120 °C for 6 h and calcined at 500 °C for 5 h to obtain the hydrogenation treatment catalyst Cat-1 of the present invention. The properties of the catalyst are shown in Table 1. Example 2

[0034] The same as example 1, except that in step (1) the Mo-Ni-P solution contains 13.0 g / 100 mL of MoO3 and 3.3 g / 100 mL of NiO, the propylene oxide has a mass concentration of 6.5%, and the amount added is 550 g, the hydrothermal treatment temperature is 140°C, and the treatment time is 2.5 hours; in step (3) the propylene oxide has a mass concentration of 5.4%, the amount added is 630 g, the hydrothermal treatment temperature is 135°C, and the treatment time is 17 hours; and in step (4) the Mo-Ni-P solution contains 10.0 g / 100 mL of MoO3 and 2.5 g / 100 mL of NiO, and the hydroprocessing catalyst Cat-2 of the present application is prepared, the properties of which are shown in Table 1. Example 3

[0035] The same as example 1, except that in step (1) the Mo-Ni-P solution contains 12.0 g / 100 mL of MoO3 and 3.0 g / 100 mL of NiO, the propylene oxide has a mass concentration of 4.5%, and the amount added is 750 g, the hydrothermal treatment temperature is 160°C, and the treatment time is 1.2 hours; in step (3) the propylene oxide has a mass concentration of 7.8%, the amount added is 460 g, the hydrothermal treatment temperature is 125°C, and the treatment time is 16 hours; and in step (4) the Mo-Ni-P solution contains 12.0 g / 100 mL of MoO3 and 3.0 g / 100 mL of NiO, and the hydroprocessing catalyst Cat-3 of the present application is prepared, the properties of which are shown in Table 1. Example 4

[0036] The same as example 1, except that in step (1) the Mo-Ni-P solution contains 13.5 g / 100 mL of MoO3 and 3.4 g / 100 mL of NiO, the propylene oxide has a mass concentration of 7.5%, and the amount added is 450 g, the hydrothermal treatment temperature is 130°C, and the treatment time is 3.0 hours; in step (3) the propylene oxide has a mass concentration of 4.3%, the amount added is 710 g, the hydrothermal treatment temperature is 155°C, and the treatment time is 19 hours; and in step (4) the Mo-Ni-P solution contains 9.0 g / 100 mL of MoO3 and 2.3 g / 100 mL of NiO, and the hydroprocessing catalyst Cat-4 of the present application is prepared, the properties of which are shown in Table 1.

[0037] Comparative Example 1

[0038] The same as example 1, except that the propylene oxide aqueous solution in steps (1) and (3) is replaced by an ethylene oxide aqueous solution of the same concentration, no worm-like particles are formed in the powder material prepared in step (1), and no sheet-like particles are formed in the "shell layer" of the alumina carrier prepared in step (3), and the comparative hydroprocessing catalyst Cat-5 is prepared, the properties of which are shown in Table 1.

[0039] Comparative Example 2

[0040] The same as Example 1, except that the propylene oxide aqueous solution in step (1) and step (3) is replaced by the same concentration of ammonia solution. No worm-like particles are formed in the powder material prepared in step (1), and no flaky particles are formed in the alumina support "shell layer" prepared in step (3). The comparative hydroprocessing catalyst Cat-6 is prepared, and the catalyst properties are shown in Table 1.

[0041] Comparative Example 3

[0042] The same as Example 1, except that the hydrothermal treatment time in step (3) is 4 hours. No flaky particles are formed in the alumina support "shell layer" prepared, and the comparative hydroprocessing catalyst Cat-7 is prepared. The catalyst properties are shown in Table 1.

[0043] Comparative Example 4

[0044] The same as Example 1, except that the boehmite in step (1) is not impregnated with the active component, and a comparative hydroprocessing catalyst Cat-8 with the same active metal content is prepared by one-step impregnation in step (4). The catalyst properties are shown in Table 1.

[0045] Table 1 Hydroprocessing catalyst properties

[0046] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Catalyst Cat-1 Cat-2 Cat-3 Cat-4 Cat-5 Cat-6 Cat-7 Cat-8 Specific surface area, m 2 / g]] 222 239 228 231 168 157 226 226 Pore volume, mL / g 0.93 0.95 0.91 0.93 0.81 0.79 0.91 0.94 8-15 nm pore content, % 62.9 64.1 63.6 65.7 50.8 49.6 60.3 57.2 Catalyst surface particle morphology Platelet Platelet Platelet Platelet Granular Granular Worm Platelet Shell platelet particle thickness, pm 0.5-0.8 0.5-0.7 0.5-0.7 0.5-0.9 — — — 0.5-0.8 Catalyst surface pore size, nm 55-240 55-255 60-260 55-280 10-120 15-130 30-180 55-245

[0047] As can be seen from Table 1, compared with the comparative hydroprocessing catalyst, the hydroprocessing catalyst prepared by the method of the present application has a higher content of pores with a diameter of 8-15 nm, and the pores on the catalyst surface are larger and more open. Example 5

[0048] A certain vacuum residue is used as the raw material, and the properties of the raw oil are as follows: the metal (Ni+V) content is 73.2 μg / g, the sulfur content is 0.61%, the nitrogen content is 0.52%, the gum content is 56.8%, the asphaltene content is 1.03%, the saturated hydrocarbon content is 23.1%, and the aromatic hydrocarbon content is 27.3%. The catalytic performances of the catalysts Cat-1-Cat-8 are evaluated on a fixed-bed residue hydroprocessing reaction device, and the reaction conditions are as follows: the reaction temperature is 380°C, the hydrogen partial pressure is 14 MPa, the liquid hourly space velocity is 0.45 h -1 , the hydrogen to oil volume ratio is 900, and the content of each impurity in the generated oil is determined after 1000 hours of reaction, the impurity removal rate is calculated, and the evaluation results are shown in Table 2.

[0049] Table 2 Comparison of hydroprocessing performances of catalysts

[0050] Catalyst number Cat-1 Cat-2 Cat-3 Cat-4 Cat-5 Cat-6 Cat-7 Cat-8 Relative demetallization rate, % 129 127 134 121 100 103 115 122 Relative desulfurization rate, % 126 123 128 122 100 99 116 118 Relative denitrification rate, % 128 130 124 135 100 107 122 121 Relative dechar rate, % 122 125 121 126 100 103 115 116

[0051] As can be seen from the data in Table 2, the hydroprocessing catalyst prepared according to the present application has high hydrogenation demetallization activity, hydrogenation desulfurization activity, hydrogenation denitrification activity and hydrogenation decarburization activity, while the hydroprocessing catalyst prepared in the comparative examples cannot simultaneously satisfy the above properties.

Claims

1. A hydrogenation catalyst, characterized in that: The catalyst comprises a core-shell structured alumina support, a first hydrogenation active metal, and a second hydrogenation active metal. The shell is grown in situ from the core phase, and the shell is a lamellar alumina grain aggregate, while the core phase is a worm-like alumina grain aggregate. The shell thickness is 0.3-1.5 μm, and the core phase diameter is 1-5 mm. The first hydrogenation active metal is Mo and / or W, and the second hydrogenation active metal is Ni and / or Co. The specific surface area of ​​the hydrogenation catalyst is 200-300 m². 2 / g, pore volume is 0.75-1.0mL / g, and pores of 8-15nm account for 55%-70% of the total pore volume; the preparation method of the hydrogenation catalyst includes the following: (1) impregnating boehmite with a solution containing the first and second hydrogenation active metals, drying and calcining the impregnated material to obtain active metal modified γ-phase alumina powder, then mixing the powder with propylene oxide aqueous solution, and then performing hydrothermal treatment, and filtering, washing and drying the treated material to obtain worm-like particles R1, then (2) The alumina carrier precursor is obtained by rolling and calcining. The obtained alumina carrier precursor is mixed with propylene oxide aqueous solution and then subjected to hydrothermal treatment. After treatment, the material is filtered, washed, dried, and calcined. Then, the first and second hydrogenation active metals are loaded to obtain the hydrogenation treatment catalyst. The concentration of the propylene oxide aqueous solution in step (1) is 2.5wt%-12wt%. The mass ratio of the amount of propylene oxide aqueous solution to the active metal modified γ-phase alumina powder is 3:1-10:

1. The sealing The heat treatment temperature is 110-180℃, and the heat treatment time is 1-3 hours; the concentration of the propylene oxide aqueous solution in step (2) is 2.5wt%-12wt%, and the mass ratio of the propylene oxide aqueous solution to the alumina carrier precursor is 3:1-10:1; the sealed heat treatment is carried out in a sealed container, the sealed heat treatment temperature is 110-180℃, and the treatment time is 14-20 hours; in step (1), the first hydrogenated active metal in the solution containing the first and second hydrogenated active metals is... The content of oxides is 11.5-15.5 g / 100 mL, the content of the second hydrogenated active metal is 2.9-3.9 g / 100 mL, and the solution volume is the saturated water absorption capacity of boehmite; the loading in step (2) is carried out by equal volume impregnation, and the content of the first hydrogenated active metal in the solution containing the first and second hydrogenated active metals is 8.5-12.5 g / 100 mL, and the content of the second hydrogenated active metal is 2.2-3.1 g / 100 mL.

2. The catalyst according to claim 1, characterized in that: The grain size of lamellar alumina is 100-600 nm; the grain size of worm-like alumina is 80-260 nm.

3. A method for preparing the hydrogenation catalyst according to claim 1 or 2, characterized in that... Includes the following: (1) The pseudoboehmite was impregnated with a solution containing the first and second hydrogenated active metals. The impregnated material was dried and calcined to obtain active metal modified γ-phase alumina powder. The powder was then mixed with propylene oxide aqueous solution and subjected to hydrothermal treatment. The treated material was filtered, washed and dried to obtain worm-like particles R1. The particles were then rolled into balls and calcined to obtain alumina carrier precursor. (2) The alumina support precursor is mixed with an aqueous solution of propylene oxide and then subjected to hydrothermal treatment. After treatment, the material is filtered, washed, dried, and calcined. Then, the first and second hydrogenation active metals are loaded to obtain the hydrogenation treatment catalyst.

4. The method according to claim 3, characterized in that: The first hydrogenation active metal in step (1) is Mo and / or W, and the second hydrogenation active metal is Ni and / or Co; the content of the first hydrogenation active metal in the solution containing the first and second hydrogenation active metals is 11.5-15.5 g / 100 mL as oxide, the content of the second hydrogenation active metal in the solution is 2.9-3.9 g / 100 mL as oxide, and the solution volume is the saturated water absorption capacity of boehmite.

5. The method according to claim 3, characterized in that: The drying and calcination in step (1) are carried out under the following conditions: drying temperature is 100-160℃ and drying time is 3-8 hours; calcination temperature is 400-650℃ and calcination time is 4-8 hours.

6. The method according to claim 3, characterized in that: The concentration of the propylene oxide aqueous solution in step (1) is 2.5wt%-12wt%; the mass ratio of the amount of propylene oxide aqueous solution to the active metal modified γ-phase alumina powder is 3:1-10:1; the sealing heat treatment temperature is 110-180℃ and the heat treatment time is 1-3 hours.

7. The method according to claim 3, characterized in that: The ball forming in step (1) is carried out in a rotary forming machine. The rotary forming machine operates under the following conditions: the tilt angle of the rotary table is 40-70º, the rotation speed of the rotary table is 10-30 rpm, and the forming time of the material in the rotary table is 10-120 min.

8. The method according to claim 3, characterized in that: The concentration of the propylene oxide aqueous solution in step (2) is 2.5wt%-12wt%, and the mass ratio of the amount of propylene oxide aqueous solution to the mass ratio of the alumina carrier precursor is 3:1-10:1; the sealed heat treatment is carried out in a sealed container, the sealed heat treatment temperature is 110-180℃, and the treatment time is 14-20 hours.

9. The method according to claim 3, characterized in that: In step (2), the first hydrogenation active metal is Mo and / or W, and the second hydrogenation active metal is Ni and / or Co. The loading is carried out by equal volume impregnation. The content of the first hydrogenation active metal as oxide in the solution containing the first and second hydrogenation active metals is 8.5-12.5 g / 100 mL, and the content of the second hydrogenation active metal as oxide is 2.2-3.1 g / 100 mL. The impregnated material is dried and calcined to obtain the hydrogenation catalyst. The drying temperature is 100-160℃ and the drying time is 3-8 hours. The calcination temperature is 450-550℃ and the calcination time is 4-8 hours.

10. The application of the hydrotreating catalyst according to claim 1 or 2 in the hydrotreating process of distillate oil.

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