Preparation method of heavy oil hydrogenation guard catalyst and demetallization catalyst

Abstract

The purpose of this invention is to provide a method for preparing a protective catalyst and a demetallization catalyst for heavy oil hydrotreating, belonging to the field of catalyst preparation technology. This invention first prepares elliptical lamellar boehmite. During the spherical forming process of the support, the content of elliptical lamellar boehmite in the mixture is adjusted to obtain an alumina support with a gradient distribution of pores. This alumina support has a high macropore content in its "shell" and wide pores. This pore structure facilitates the diffusion of large molecular reactants into the interior of the support. At the same time, the support surface has strong anti-clogging ability.

Description

Technical Field

[0001] This invention belongs to the field of catalyst preparation technology, specifically relating to a method for preparing a heavy oil hydrogenation protection catalyst and a demetallization catalyst. Background Technology

[0002] With increasingly stringent environmental regulations and the increasing heaviness of crude oil, efficient conversion of heavy oil has become a significant trend in refining technology development. Heavy oil includes atmospheric and vacuum residue, heavy crude oil, oil sands, and synthetic heavy oil products. This oil contains large amounts of heavy metals (such as Ca, Fe, Ni, V), sulfur, nitrogen, and other impurities, and also has high asphalt and gum content. Fixed-bed residue hydrotreating technology is an effective means to achieve efficient conversion of heavy oil. Residue oil has high viscosity, high impurity content, and complex molecular composition, making hydrotreating reactions challenging. It requires effective removal of impurities such as metals, sulfur, nitrogen, and residual carbon through catalytic reactions. A single catalyst is insufficient; a matching packing system using catalysts with different functions, shapes, and sizes is necessary to achieve high activity and long-term industrial operation. Therefore, current heavy oil hydrotreating units are pre-loaded with hydroprotective agents and hydrodemetallization catalysts.

[0003] CN106622307A discloses a hydrogenation protective agent, its preparation method, and its application. The protective agent contains an active metal component and a modified hydrogenation catalyst support. The modified hydrogenation catalyst support is prepared by a method comprising: repeatedly impregnating and drying a hydrothermally treated support, and calcining the final dried product. The catalyst support prepared by this method exhibits a layered distribution of acidic promoters, and the catalyst demonstrates good calcium and iron removal capabilities. However, the removal capabilities of nickel and vanadium need further improvement, and the catalyst surface has poor pore openness.

[0004] CN111821990A discloses a support for a residual oil hydrotreating protective agent, a catalyst, and a method for preparing the same. The support is a modified alumina-based support containing a modifying element and a first hydrotreating active metal component. The modified alumina-based support comprises a main modified alumina and rod-shaped modified alumina. The main modified alumina is alumina with micron-sized pores, wherein at least some of the rod-shaped modified alumina is distributed on the outer surface of the main modified alumina and within micron-sized pores with a pore diameter D of 5-10 μm. The modifying element is vanadium, and the first hydrotreating active metal component is molybdenum. The alumina support prepared by this method has good surface pore connectivity; however, the rod-shaped particles on the surface of the catalyst prepared using this alumina support are easily detached during catalyst loading and hydrotreating reactions, causing catalyst bed blockage. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing a heavy oil hydrotreating protective catalyst and a demetallization catalyst. The catalyst prepared by this method has a core-shell structure with a gradient distribution of pore structure and active components. During hydrotreating, it has high Ca and Fe removal capabilities as well as high Ni and V removal capabilities.

[0006] The present invention adopts the following technical solution:

[0007] A method for preparing a heavy oil hydrotreating protective catalyst and a demetallization catalyst includes the following steps:

[0008] The first step is to prepare elliptical lamellar pseudoboehmite P1;

[0009] The second step involves impregnating pseudoboehmite P1 with a phosphorus-containing solution and drying it. The treated material is then mixed with pseudoboehmite P2, and the mixture is ball-rolled to obtain alumina carrier precursor S1.

[0010] The third step involves mixing pseudoboehmite P1 and pseudoboehmite P3, then mixing the alumina carrier precursor S1 with the mixture, and continuing to roll-spherical molding. The molded material is then dried and calcined to obtain the alumina carrier.

[0011] The fourth step involves sequentially impregnating the alumina support with impregnation solutions A and B containing molybdenum and nickel. The impregnated material is then dried and calcined to obtain the heavy oil hydrogenation protective catalyst and the demetallization catalyst.

[0012] Further, the preparation method of the elliptical layered pseudoboehmite P1 in the first step is as follows: the pseudoboehmite is roasted; the treated material is immersed in organic alkali solution I for a first hydrothermal treatment; the material after the first hydrothermal treatment is immersed in organic alkali solution II for a second hydrothermal treatment; the treated material is dried to obtain elliptical layered pseudoboehmite.

[0013] Further, the pseudoboehmite is preferably prepared by the aluminum sulfate-sodium aluminate method, and the calcination temperature is 450-550℃, with a calcination time of 1-6 hours; the organic base solution I includes one of tetramethylammonium hydroxide and tetrapropylammonium hydroxide, preferably tetraethylammonium hydroxide, and the mass concentration of the organic base in organic base solution I is 0.8%-2.0%; the primary hydrothermal treatment is carried out in a sealed container, preferably a high-pressure reactor, with a primary hydrothermal treatment temperature of 80-120℃ and a treatment time of 1-4 hours; the organic base solution II includes one of tetramethylammonium hydroxide and tetrapropylammonium hydroxide, preferably tetraethylammonium hydroxide; organic base solution II and organic base solution I can be the same or different, preferably the same. The mass concentration of the organic base in organic base solution II is 3.5%-12.5%. The secondary hydrothermal treatment is carried out in a sealed container, preferably a high-pressure reactor. The secondary hydrothermal treatment temperature is 140-180℃, and the treatment time is 4-10 hours.

[0014] Furthermore, the elliptical lamellar pseudoboehmite P1 particles are elliptical lamellar in shape, with a length of 2-5 μm, a width of 1-2 μm, and a thickness of 100-200 nm.

[0015] Furthermore, the phosphorus-containing solution in the second step includes one or a mixture of phosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, and ammonium phosphate, preferably an ammonium phosphate solution, wherein the concentration of ammonium phosphate in the solution is 0.2-0.5M, and the amount of phosphorus-containing solution used is such that the solid material is saturated with adsorption; the drying temperature is 100-160℃, and the drying time is 1-6 hours.

[0016] Furthermore, the pseudoboehmite P2 particles mentioned in the second step are in granular form, preferably pseudoboehmite with a pore size greater than 10 nm.

[0017] Furthermore, in the second step, the mass ratio of pseudoboehmite P1 to pseudoboehmite P2 is 1:9-1:4.

[0018] Furthermore, the spherical forming described in the second step is carried out in a rotary forming machine, with the following operating conditions: the tilt angle of the rotary table is 35-70°, the rotation speed of the rotary table is 10-30 rpm, the forming time of the material in the rotary table is 30-120 min, and the radius of the alumina carrier precursor S1 is 0.5r-0.8r, where r is the radius of the final alumina material.

[0019] Furthermore, the pseudoboehmite P3 particles mentioned in the third step are in granular form, preferably pseudoboehmite with a pore size greater than 15 nm.

[0020] Furthermore, in the third step, the mass ratio of pseudoboehmite P1 to pseudoboehmite P3 is 7:3-9:1.

[0021] Furthermore, the ball forming described in the third step is carried out in a rotary forming machine, with the following operating conditions: the tilt angle of the rotary table is 35-70°, the rotation speed of the rotary table is 10-30 rpm, and the forming time of the material in the rotary table is 20-120 min.

[0022] Furthermore, in the third step, the drying temperature is 100℃-180℃ and the drying time is 1-8 hours; the calcination temperature is 500-750℃ and the calcination time is 2-8 hours.

[0023] Further, in step four, the molybdenum-nickel-containing impregnation solution A is a Mo-Ni-P solution, with a molybdenum content of 7.5%-12.5 g / 100 mL (calculated as oxide) and a nickel content of 2%-4.5 g / 100 mL (calculated as oxide). The amount of impregnation solution A is 60%-90% of the saturated water absorption capacity of the alumina carrier. The molybdenum-nickel-containing impregnation solution B is a Mo-Ni-P solution, with a molybdenum content of 3.5%-7.5 g / 100 mL (calculated as oxide) and a nickel content of 0.8%-2.5 g / 100 mL (calculated as oxide). The amount of impregnation solution B is 10%-40% of the saturated water absorption capacity of the alumina carrier.

[0024] Furthermore, in the fourth step, the drying temperature is 100-160℃ and the drying time is 2-8 hours, and the calcination temperature is 450-550℃ and the calcination time is 4-6 hours.

[0025] The beneficial effects of this invention are as follows:

[0026] 1. This invention first prepares elliptical lamellar pseudoboehmite. During the carrier spheroidizing process, the content of elliptical lamellar pseudoboehmite in the mixture is adjusted to obtain an alumina carrier with a gradient distribution of pores. This alumina carrier has a high macropore content in its "shell" and wide pores. This pore structure facilitates the diffusion of macromolecular reactants into the carrier interior. At the same time, the carrier surface has strong anti-clogging ability.

[0027] 2. The “core layer” of elliptical lamellar pseudoboehmite is modified with phosphorus, and the phosphorus is evenly distributed on the surface of the lamellar particles, which effectively increases the acid content on the surface of the corresponding macropores, improves the ability of the catalyst “core layer” to hydrogenate Ni and V, and the channels formed by the accumulation of lamellar particles have strong metal-carrying capacity.

[0028] 3. The prepared catalyst has a low metal content in the "shell" and a high metal content in the "core". During hydrogenation, the "shell" is beneficial for filtering impurities in the reaction feedstock and removing metal impurities such as Ca and Fe, while the "core" is beneficial for removing metal impurities such as Ni and V. This results in the final catalyst having a high ability to remove metal impurities such as Ca, Fe and Ni and V. Attached Figure Description

[0029] Figure 1 SEM image of the elliptical lamellar pseudoboehmite prepared in Example 1.

[0030] Figure 2 This is a SEM image of the cross-sectional "shell" of the alumina prepared in Example 1.

[0031] Figure 3 This is a SEM image of the cross-sectional "core layer" of the alumina prepared in Example 1. Detailed Implementation

[0032] The technical solutions 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.

[0033] Sample pore structure characterization: The sample pore structure was characterized using a Micromeritics Trister 3000 nitrogen physisorption instrument.

[0034] Characterization of pore diameters greater than 100 nm: The pore distribution of the samples was characterized using a fully automated mercury porosimeter (AutoPore 9500) from the USA.

[0035] Sample microstructure characterization: The microstructure of the samples was characterized using a Hitachi SU8220 scanning electron microscope (SEM).

[0036] The method for determining the average pore size of the "shell" and "core" layers of the catalyst in this invention is as follows: First, the pore volume, specific surface area, and average pore diameter of the sample are determined using the low-temperature nitrogen adsorption method (BET). Then, a certain amount of sample is placed in a catalyst abrasion apparatus for abrasion treatment, and a certain amount of quartz sand is added to increase the abrasion rate. When the particle size of the sample is reduced to a certain extent after abrasion, the weight loss of the sample is measured, and its pore structure is measured again. Based on the relationship that the total pore volume and specific surface area of ​​the sample are equal to the sum of its parts, the pore volume and specific surface area of ​​the abraded portion can be calculated. Simultaneously, 40-80 samples are measured, and then the average pore diameter is calculated.

[0037] Preparation of elliptical lamellar pseudoboehmite:

[0038] Example 1

[0039] (1) A suitable amount of boehmite (prepared by aluminum sulfate-sodium aluminate method) was calcined at 450℃ for 4 hours.

[0040] After calcination, the material was placed in a polytetrafluoroethylene-lined autoclave, and a 1.2 wt% tetraethylammonium hydroxide solution was added to completely submerge the powder. The mixture was stirred for 45 minutes, and after sealing the autoclave, it was hydrothermally treated at 105℃ for 2 hours. The treated material was then filtered. The filter cake was again placed in the autoclave reaction liner, and a 7 wt% tetraethylammonium hydroxide solution was added to completely submerge the material. The mixture was stirred for 45 minutes, and after sealing the autoclave, it was hydrothermally treated at 165℃ for 6.5 hours. The treated material was then washed and filtered, and the filter cake was dried at 140℃ for 6 hours to obtain elliptical, layered pseudoboehmite. The scanning electron microscope image of the sample is shown below. Figure 1 .

[0041] (2) Weigh 85 g of the elliptical layered pseudoboehmite from step (1), saturate the material with a 0.3 M ammonium phosphate solution, and dry the material at 120 °C for 4 hours after impregnation. Add 500 g of pseudoboehmite P2 (with a pore size of 12.5 nm) to the dried material and mix evenly. Then place the mixture in a rotary molding machine, adjust the tilt angle of the rotary table to 45°, and the rotation speed of the rotary table to 20 rpm; and spray an appropriate amount of 1% acetic acid aqueous solution onto the material in the rotary table. The molding time of the material in the rotary table is 70 min to obtain spherical alumina carrier precursor S1;

[0042] (3) Weigh 500 g of pseudoboehmite P3 (with a pore size of 17.5 nm) and 1500 g of the elliptical lamellar pseudoboehmite from step (1) and mix them evenly. Place the mixture and the spherical alumina carrier precursor S1 prepared in step (2) into a rotary molding machine, adjust the tilt angle of the rotary table to 45°, and the rotation speed of the rotary table to 20 rpm; spray an appropriate amount of 1% acetic acid aqueous solution onto the material in the rotary table, and the material is molded in the rotary table for 35 min. Dry the obtained spherical carrier at 140°C for 6 h and calcine at 650°C for 4 h to obtain the alumina carrier of the present invention.

[0043] (4) Weigh 100 g of the alumina support from step (3) and place it in a spray impregnation pot. Spray the alumina support with 74 mL of a Mo-Ni-P solution with a molybdenum oxide concentration of 9.0 g / 100 mL and a nickel oxide concentration of 2.2 g / 100 mL until the support is saturated with adsorption. Dry the impregnated material at 140 °C for 5 hours and calcine at 500 °C for 5 hours to obtain catalyst C-1 of the present invention. The properties of the catalyst are shown in Table 1. The scanning electron microscope image of the cross-sectional "shell" of the catalyst is shown in Table 1. Figure 2 The scanning electron microscope image of the "nuclear layer" is shown below. Figure 3 .

[0044] Example 2

[0045] Same as Example 1, except that in step (1), the concentration of tetraethylammonium hydroxide in the first hydrothermal treatment is 1.5 wt%, the hydrothermal treatment temperature is 95℃, and the treatment time is 3 hours. In the second hydrothermal treatment, the concentration of tetraethylammonium hydroxide is 9 wt%, the hydrothermal treatment temperature is 155℃, and the treatment time is 8 hours. In step (2), the concentration of ammonium phosphate solution is 0.35M, the amount of elliptical layered pseudoboehmite added is 99 grams, and the spheroidizing time is 75 min. In step (3), the amount of elliptical layered pseudoboehmite added is 2000 grams, and the spheroidizing time is 30 min. Step (4) First, spray the alumina support with 78 mL of Mo-Ni-P solution with a molybdenum oxide concentration of 8.5 g / 100 mL and a nickel oxide concentration of 2.1 g / 100 mL. Then, spray the alumina support with Mo-Ni-P solution with a molybdenum oxide concentration of 5.0 g / 100 mL and a nickel oxide concentration of 1.1 g / 100 mL until the support is saturated with adsorption, and obtain catalyst C-2. The properties of the catalyst are shown in Table 1.

[0046] Example 3

[0047] Same as Example 1, except that in step (1), the concentration of tetraethylammonium hydroxide during the first hydrothermal treatment is 0.9 wt%, the hydrothermal treatment temperature is 115℃, and the treatment time is 1.5 hours. In the second hydrothermal treatment, the concentration of tetraethylammonium hydroxide is 4 wt%, the hydrothermal treatment temperature is 175℃, and the treatment time is 5 hours. In step (2), the concentration of ammonium phosphate solution is 0.45 M, the amount of elliptical layered pseudoboehmite added is 71 g, and the spheroidizing time is 80 min. In step (3), the amount of elliptical layered pseudoboehmite added is 2800 g, and the spheroidizing time is 25 min. Step (4) First, the alumina support is sprayed with 83 mL of Mo-Ni-P solution with a molybdenum oxide concentration of 8.0 g / 100 mL and a nickel oxide concentration of 2.0 g / 100 mL. Then, the alumina support is sprayed with Mo-Ni-P solution with a molybdenum oxide concentration of 5.5 g / 100 mL and a nickel oxide concentration of 1.3 g / 100 mL until the support is saturated with adsorption, thus obtaining catalyst C-3. The properties of the catalyst are shown in Table 1.

[0048] Example 4

[0049] Same as Example 1, except that in step (1), the concentration of tetraethylammonium hydroxide during the first hydrothermal treatment is 1.8 wt%, the hydrothermal treatment temperature is 85℃, and the treatment time is 3.5 hours. In the second hydrothermal treatment, the concentration of tetraethylammonium hydroxide is 12 wt%, the hydrothermal treatment temperature is 145℃, and the treatment time is 9.5 hours. In step (2), the concentration of ammonium phosphate solution is 0.25 M, the amount of elliptical layered pseudoboehmite added is 113 g, and the spheroidizing time is 65 min. In step (3), the amount of elliptical layered pseudoboehmite added is 1200 g, and the spheroidizing time is 40 min. Step (4) First, spray the alumina support with 70 mL of Mo-Ni-P solution with a molybdenum oxide concentration of 9.5 g / 100 mL and a nickel oxide concentration of 2.4 g / 100 mL. Then, continue to spray the alumina support with Mo-Ni-P solution with a molybdenum oxide concentration of 4.0 g / 100 mL and a nickel oxide concentration of 0.9 g / 100 mL until the support is saturated with adsorption, and obtain catalyst C-4. The properties of the catalyst are shown in Table 1.

[0050] Comparative Example 1

[0051] Same as Example 1, except that the tetraethylammonium hydroxide solution in the first and second hydrothermal treatments in step (1) was replaced with an ammonia solution of the same concentration. No elliptical layered particles were observed to be generated in the material after the hydrothermal treatment in step (1). Comparative catalyst C-5 was obtained, and the properties of the catalyst are shown in Table 1.

[0052] Comparative Example 2

[0053] Same as Example 1, except that the tetraethylammonium hydroxide solution in the first and second hydrothermal treatments in step (1) was replaced with sodium hydroxide solution of the same concentration. No elliptical layered particles were observed to be generated in the material after the hydrothermal treatment in step (1). Comparative catalyst C-6 was obtained, and the properties of the catalyst are shown in Table 1.

[0054] Comparative Example 3

[0055] Same as Example 1, except that in step (2) spheroidizing, all raw materials used are pseudoboehmite P2, and in step (3) spheroidizing, all raw materials used are pseudoboehmite P3, and comparative catalyst C-7 is obtained. The properties of the catalyst are shown in Table 1.

[0056] Table 1 Catalyst Properties

[0057]

[0058] From the data in Table 1 and Figure 2 It can be seen that the catalyst prepared by the method of the present invention has a large surface pore size, a high content of 0.5-1μm pores, and an open surface pore structure, which is conducive to the diffusion of macromolecular reactants.

[0059] Example 5

[0060] The catalyst prepared according to this invention and the catalyst prepared in the comparative example were respectively loaded into a fixed-bed hydrogenation reactor. The feedstocks were processed (see Table 2). The experimental conditions were as follows: reaction temperature 385℃, hydrogen-to-oil volume ratio 800, and liquid hourly space velocity 1.0 h⁻¹. -1 The hydrogen partial pressure was 14.0 MPa, and the impurity removal properties were obtained after 3000 hours of continuous operation. See Table 3 for the properties of the impurity removal.

[0061] Table 2 Properties of Crude Oil

[0062]

[0063] Table 3 Evaluation results of the catalyst

[0064]

[0065] As can be seen from the results in Table 3, compared with the comparative catalyst, the hydrogenation protection catalyst and demetallization catalyst prepared by this method can effectively remove Ca and Fe impurities while having a high Ni and V removal rate. At the same time, the catalyst has good activity stability.

Claims

1. A method for preparing a heavy oil hydrotreating protective catalyst and a demetallization catalyst, characterized in that: Includes the following steps: The first step is to prepare elliptical lamellar pseudoboehmite P1. The preparation method of elliptical lamellar pseudoboehmite P1 is as follows: the pseudoboehmite is roasted; the treated material is immersed in organic alkali solution I for a first hydrothermal treatment; the material after the first hydrothermal treatment is immersed in organic alkali solution II for a second hydrothermal treatment; the treated material is dried to obtain elliptical lamellar pseudoboehmite. The pseudoboehmite is prepared by the aluminum sulfate-sodium aluminate method. The calcination temperature is 450-550℃, and the calcination time is 1-6 hours. The organic base solution I includes one of tetramethylammonium hydroxide and tetrapropylammonium hydroxide, and the mass concentration of the organic base in the organic base solution I is 0.8%-2.0%. The primary hydrothermal treatment is carried out in a sealed container at a temperature of 80-120℃ for 1-4 hours. The organic base solution II includes one of tetramethylammonium hydroxide and tetrapropylammonium hydroxide. The organic base solution II may be the same as or different from the organic base solution I, and the mass concentration of the organic base in the organic base solution II is 3.5%-12.5%. The secondary hydrothermal treatment is carried out in a sealed container at a temperature of 140-180℃ for 4-10 hours. The second step involves impregnating pseudoboehmite P1 with a phosphorus-containing solution and drying it. The treated material is then mixed with pseudoboehmite P2, and the mixture is ball-rolled to obtain alumina carrier precursor S1. The pseudoboehmite P2 particles are granular in shape and have a pore size greater than 10 nm. The mass ratio of pseudoboehmite P1 to pseudoboehmite P2 is 1:9-1:4; The third step involves mixing pseudoboehmite P1 and pseudoboehmite P3, then mixing the alumina carrier precursor S1 with the mixture, and continuing to roll-spherical molding. The molded material is then dried and calcined to obtain the alumina carrier. The pseudoboehmite P3 particles are granular in shape and have a pore size greater than 15 nm. The mass ratio of pseudoboehmite P1 to pseudoboehmite P3 is 7:3-9:1; The fourth step involves sequentially impregnating the alumina support with impregnation solutions A and B containing molybdenum and nickel. The impregnated material is then dried and calcined to obtain a heavy oil hydrotreating protective catalyst and a demetallization catalyst. The molybdenum-nickel impregnation solution A is a Mo-Ni-P solution, in which the molybdenum content (calculated as oxide) is 7.5%-12.5 g / 100 mL and the nickel content (calculated as oxide) is 2%-4.5 g / 100 mL. The amount of impregnation solution A is 60%-90% of the saturated water absorption capacity of the alumina carrier. The molybdenum-nickel impregnation solution B is a Mo-Ni-P solution, in which the molybdenum content (calculated as oxide) is 3.5%-7.5 g / 100 mL and the nickel content (calculated as oxide) is 0.8%-2.5 g / 100 mL. The amount of impregnation solution B is 10%-40% of the saturated water absorption capacity of the alumina carrier.

2. The method for preparing a heavy oil hydrotreating protective catalyst and a demetallization catalyst according to claim 1, characterized in that: The elliptical lamellar pseudoboehmite P1 particles are elliptical lamellar in shape, with a length of 2-5 μm, a width of 1-2 μm, and a thickness of 100-200 nm.

3. The method for preparing a heavy oil hydrotreating protective catalyst and a demetallization catalyst according to claim 1, characterized in that: The phosphorus-containing solution mentioned in the second step includes one or a mixture of phosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, and ammonium phosphate. The amount of phosphorus-containing solution used is such that the solid material is saturated with adsorption. The drying temperature is 100-160℃ and the drying time is 1-6 hours.

4. The method for preparing a heavy oil hydrotreating protective catalyst and a demetallization catalyst according to claim 1, characterized in that: The spherical forming described in the second step is carried out in a rotary forming machine. The operating conditions are as follows: the tilt angle of the rotary table is 35-70°, the rotation speed of the rotary table is 10-30 rpm, the forming time of the material in the rotary table is 30-120 min, and the radius of the alumina carrier precursor S1 is 0.5r-0.8r, where r is the radius of the final alumina material.

5. The method for preparing a heavy oil hydrotreating protective catalyst and a demetallization catalyst according to claim 1, characterized in that: The ball forming described in the third step is carried out in a rotary forming machine. The operating conditions are: the tilt angle of the rotary table is 35-70°, the rotation speed of the rotary table is 10-30 rpm, and the forming time of the material in the rotary table is 20-120 min. The drying temperature in the third step is 100℃-180℃, and the drying time is 1-8 hours; the calcination temperature is 500-750℃, and the calcination time is 2-8 hours.

6. The method for preparing a heavy oil hydrotreating protective catalyst and a demetallization catalyst according to claim 1, characterized in that: The drying temperature in step four is 100-160℃, and the drying time is 2-8 hours. The calcination temperature is 450-550℃, and the calcination time is 4-6 hours.

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