A method for preparing a heavy oil hydrodemetallization catalyst

Abstract

The application discloses a preparation method of a heavy oil hydroprocessing catalyst, and comprises the following steps: (1) uniformly mixing pseudo-boehmite P1 and a physical pore-expanding agent, and rolling the mixture to obtain spherical precursor S0; (2) uniformly mixing pseudo-boehmite P2, activated carbon impregnated with aluminum nitrate and active metal components Q1, and obtaining W1, then mixing W1 with S0, and rolling the mixture to obtain spherical precursor S1; (3) uniformly mixing pseudo-boehmite P3 and a proper amount of activated carbon impregnated with aluminum nitrate and active metal components Q2, and obtaining W2, then mixing W2 with S1, and rolling the mixture to obtain precursor S2; and (4) sealingly heat-treating S2 in an epoxypropane aqueous solution, performing solid-liquid separation, drying, and calcining to obtain an aluminum oxide carrier, and loading a hydrogenation active component to obtain a catalyst product. The catalyst is rich in spherical cavities, and macropores on the surface and inside are gradient-distributed; the spherical cavities have high catalytic activity, and are suitable for the field of heavy oil hydroprocessing.

Description

TECHNICAL FIELD

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

[0002] Fixed bed residual oil hydrogenation process technology is mature, widely used, and is an effective means to realize efficient conversion of heavy oil at present. Residual oil is rich in most of the sulfur, nitrogen, metals (mainly nickel and vanadium) and the like in crude oil. Residual oil hydrogenation removes metal, sulfur, nitrogen and the like impurities under the action of a catalyst under high temperature and high pressure conditions, to provide high-quality raw materials for downstream catalytic cracking. At present, residual oil hydroprocessing catalysts generally include protective catalysts, demetallization catalysts, desulfurization catalysts and denitrogenation catalysts. Among them, the role of the residual oil hydrodemetallization catalyst is to remove Ni, V and the like metals in the residual oil, and to protect the desulfurization catalyst. It not only removes metal impurities in the feed, but also must accommodate as much as possible these metal and coke impurities.

[0003] CN104646008A discloses a poor-quality heavy oil hydrodesulfurization and demetallization catalyst and a preparation method thereof. The catalyst uses alumina as a carrier, and uses Group VIII and Group VIB elements, particularly Ni-Mo, as active components. The catalyst has a pore volume of 0.61-0.70 mL / g, a specific surface area of 155-200 m 2 / g, and an average pore diameter of 13.0-18.0 nm. The preparation method of the catalyst is to treat the carrier particles after molding and calcination with an acid solution with continuously increasing concentration. Although this method can make the average pore diameter of the final catalyst gradually increase from the center to the outer surface along the radial direction of the catalyst particle to a certain extent, this treatment method is difficult to form larger pores on the surface of the carrier.

[0004] CN106669853A discloses a preparation method of a spherical modified alumina carrier. The spherical modified alumina carrier has the following properties: having a double pore distribution, a pore size of 10-15 nm and 15-30 nm; wherein the pore distribution of 10-15 nm accounts for 35%-40% of the total pore volume, and the pore distribution of 15-30 nm accounts for 30%-35% of the total pore volume; the amount of additives is 2%-5% by weight based on the weight of the carrier, and the additive concentration gradually increases from the center of the carrier particle to the outer surface, wherein the additive content at 1 / 4R is 0.5wt%-1.0wt%, the additive content at 1 / 2R is 1.5wt%-2.0wt%, and the additive content at R is 2.5wt%-3.0wt%, wherein R is the radius of the carrier particle with the center of the spherical modified alumina carrier as the initial point; wherein the additive is one of the following combinations of I, II and III: I-fluorine and phosphorus, II-fluorine and boron, III-fluorine, phosphorus and boron. The alumina carrier prepared by the method has a gradient distribution of additives, but the pore gradient distribution is poor, which is not conducive to the diffusion of macromolecular reactants.

[0005] CN110935461A discloses a preparation method of a heavy oil hydrodemetallization catalyst. The preparation method of the catalyst comprises: (1) mixing and kneading a physical pore expander, pseudo-boehmite and an active metal component, drying, and calcining to obtain a modified alumina carrier SI; (2) unsaturatedly spraying and impregnating SI with a hydroactive component impregnation solution I, and then drying and calcining to obtain a modified alumina carrier SII; (3) mixing SII, ammonium bicarbonate and water, and then performing sealed heat treatment, and then drying and calcining the material after heat treatment to obtain a carrier SIII; (4) supersaturatingly impregnating carrier SIII with a hydroactive component impregnation solution II, and then drying and calcining to obtain the catalyst. The catalyst prepared by the method has a rod-like structure on the surface, the formed pore is open, the metal deposition resistance and the carbon deposition resistance of the catalyst are improved, but the rod-like alumina grown on the surface is easy to fall off, and the combination of the rod-like alumina with the main body alumina needs to be further improved. SUMMARY

[0006] In view of the deficiencies in the prior art, the present application provides a preparation method of a heavy oil hydroprocessing catalyst. The catalyst is rich in spherical cavities, and the macropores are gradiently distributed from the surface to the inside, which is conducive to the diffusion of reactant molecules to the inside of the catalyst. The spherical cavity has high catalytic activity, strong metal impurity and carbon deposition resistance, and the catalyst has high hydrodemetallization and desulfurization activity and activity stability, and is suitable for the field of heavy oil hydroprocessing.

[0007] The preparation method of the heavy oil hydroprocessing catalyst comprises the following steps: (1) uniformly mixing pseudo-boehmite P1 and a physical pore-expanding agent, and performing ball rolling to obtain spherical precursor S0; (2) uniformly mixing pseudo-boehmite P2, a proper amount of microspherical activated carbon Q1 impregnated with aluminum nitrate solution A and active metal component solution I, mixing the material W1 with the spherical precursor S0, and performing ball rolling to obtain spherical precursor S1; (3) uniformly mixing pseudo-boehmite P3, a proper amount of microspherical activated carbon Q2 impregnated with aluminum nitrate solution B and active metal component solution II, mixing the material W2 with the spherical precursor S1, performing ball rolling, and then drying and calcining to obtain precursor S2; and (4) sealingly treating the precursor S2 in step (3) in an epoxypropane aqueous solution, performing solid-liquid separation on the treated material, drying and calcining the solid-phase material to obtain an alumina carrier, and then loading a hydrogenation active component to obtain a catalyst product.

[0008] In the method, the ball rolling is performed in a rotating disc forming machine, and the rotating operation conditions of the rotating disc forming machine are that the inclination angle of the rotating disc is 40-70°, and the rotating speed of the rotating disc is 10-30 rpm; and the forming time of the material in the rotating disc is 5-120 min. The radius of the spherical precursor S0 is 0.2r-0.6r, and the radius of the spherical precursor S1 is 0.5r-0.8r, wherein r is the radius of the final spherical alumina material, that is, the straight-line distance from the center of the sphere to the outer surface. A water solution containing a glue solvent is sprayed into the material during the 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 and acetic acid, and the mass concentration of the solution is 1%-3%, and the water solution of acetic acid is preferred.

[0009] In the method, the particle form of the pseudo-boehmite P1 in step (1) is granular, which can be a commercially available product or a pseudo-boehmite prepared by an acid precipitation method, an alkali precipitation method, an alcohol aluminum hydrolysis method or the like, and preferably a pseudo-boehmite with a pore diameter of 8.5-10 nm.

[0010] In the method, the physical pore-expanding agent in step (1) is one or more of activated carbon, wood chips, carbon black, urea, propylene glycol glycerol, triethylene glycol, melamine, polyethylene glycol, polyethylene oxide, methyl cellulose, polyoxyethylene, polyacrylamide and starch. The mass ratio of the physical pore-expanding agent to the pseudo-boehmite P1 is 1:20-1:10.

[0011] In the method, the concentration of the aluminum nitrate solution A in step (2) is 10wt%-20wt%, and the solution is used in an amount to saturate the adsorption of the microspherical activated carbon.

[0012] In the method, the active metal component solution I in step (2) is a solution containing molybdenum and nickel, the molybdenum concentration in the solution is 1.5-3 g / 100 mL, the nickel concentration in the solution is 0.4-1 g / 100 mL, and the solution is used in an amount to saturate the microspherical activated carbon.

[0013] In the method, the impregnation sequence of the aluminum nitrate solution A and the active metal component solution I in step (2) is not particularly limited, and the aluminum nitrate solution A can be impregnated first and then the active metal component solution I, or the active metal component solution I can be impregnated first and then the aluminum nitrate solution A. After each impregnation, the microspherical activated carbon generally needs to be dried, the drying temperature is 60-160°C, and the drying time is 1-5 hours.

[0014] In the method, the pseudo-boehmite P2 in step (2) has a particle morphology, preferably a pseudo-boehmite with a mesopore diameter of 10-15 nm, and the microspherical activated carbon Q1 has a diameter of 1-5 microns. The microspherical activated carbon can be prepared by existing methods or purchased, and the mass ratio of the microspherical activated carbon to the pseudo-boehmite P2 is 1:6.7-1:12.5.

[0015] In the method, the pseudo-boehmite P3 in step (3) has a particle morphology, preferably a pseudo-boehmite with a mesopore diameter greater than 15 nm, which can be prepared by existing technologies or purchased.

[0016] In the method, the aluminum nitrate solution B in step (3) has a concentration of 20wt%-30wt%, and the solution is used in an amount to saturate the microspherical activated carbon.

[0017] In the method, the active metal component solution II in step (3) is a solution containing molybdenum and nickel, the molybdenum concentration in the solution is 3-4.5 g / 100 mL, the nickel concentration in the solution is 0.8-1.2 g / 100 mL, and the solution is used in an amount to saturate the microspherical activated carbon.

[0018] In the method, the impregnation sequence of the aluminum nitrate solution B and the active metal component solution II in step (3) is not particularly limited, and the aluminum nitrate solution B can be impregnated first and then the active metal component solution II, or the active metal component solution II can be impregnated first and then the aluminum nitrate solution B. After each impregnation, the microspherical activated carbon generally needs to be dried, the drying temperature is 60-160°C, and the drying time is 1-5 hours.

[0019] In the method, the microspherical activated carbon Q2 in step (3) has a diameter of 5-10 microns. The microspherical activated carbon can be prepared by existing methods or purchased, and the mass ratio of the microspherical activated carbon to the pseudo-boehmite P3 is 1:5-1:10.

[0020] In the method, the drying temperature in step (3) is 100-160℃, and the drying time is 2-8 hours; the calcination is carried out in an oxygen atmosphere, and the calcination temperature is 450-600℃, and the calcination time is 4-8 hours.

[0021] In the method, the mass percentage concentration of the propylene oxide aqueous solution in step (4) is 2.5%-12%, preferably 4%-8%, and the mass ratio of the propylene oxide aqueous solution to the alumina carrier precursor is 3:1-10:1, preferably 4:1-8:1.

[0022] In the method, the sealing heat treatment in step (4) is preferably carried out in a sealed autoclave, and the sealing heat treatment is preferably two-step sealing heat treatment, i.e., first low-temperature sealing heat treatment at 60-100℃ for 1-4 hours, and then sealing heat treatment at 110-180℃, preferably 120-160℃, for 14-20 hours.

[0023] In the method, the drying temperature in step (4) is 100-160℃, and the drying time is 2-8 hours; the calcination temperature is 500-750℃, and the calcination time is 4-8 hours, and the calcination is carried out in an oxygen-containing atmosphere, preferably an air atmosphere.

[0024] In the method, the loading mode in step (4) can adopt an impregnation mode, and the Mo content in the impregnation solution of the hydrogenation active component is 7.5%-13.5g / 100mL in terms of metal oxide, and the Ni content is 2.1-4.5g / 100mL in terms of metal oxide.

[0025] In the method, the drying temperature in step (4) 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.

[0026] Compared with the prior art, the present application has the following advantages:

[0027] (1) In the present application, the mixture is adjusted to prepare an alumina carrier precursor with a gradient distribution of micron-sized spherical cavities. The alumina carrier precursor is placed in a propylene oxide aqueous solution for sealed hydrothermal treatment. During low-temperature sealing heat treatment, propylene oxide is hydrolyzed to form an alcohol solution, and the solution becomes weakly alkaline. During high-temperature sealing hydrothermal treatment, the aluminum oxide compounds formed by calcination of the aluminum oxide grains on the surface of the alumina carrier, the micron-sized cavity surface, and the aluminum nitrate in the micron-sized cavity grow in situ to form flaky aluminum oxide grains in an alkaline and alcohol solution environment. The flaky aluminum oxide on the outer surface of the carrier accumulates to form open channels with a diameter of 40-300nm, and the flaky aluminum oxide in the micron-sized cavity accumulates to form through channels with a diameter of 50-100nm. This channel structure is beneficial to the diffusion of macromolecular reactants into the carrier.

[0028] (2) In this invention, micron-sized spherical activated carbon of different sizes is impregnated with aluminum nitrate solution of different concentrations and solution containing active metal components. During calcination, aluminum nitrate decomposes to form corresponding aluminum oxide compounds and active metal components, which are oriented and anchored into the micron-sized spherical cavity of the support. During in-situ growth under hydrothermal treatment, the active metal components work together with the rehydration process of alumina grains to improve the interaction between the active metal components and the alumina support, thereby increasing the activity of the catalyst.

[0029] (3) By directional regulation of active metal components and plate alumina, the active metal content in the channels formed by the accumulation of plate particles in the spherical cavity of the catalyst is increased. The active metal components are highly matched with the channel structure of the catalyst, so that the catalyst has high activity and high resistance to metal deposition. Attached Figure Description

[0030] Figure 1 is a SEM image of the outer surface of the alumina carrier prepared in Example 1.

[0031] Figure 2 This is a cross-sectional SEM image of the alumina carrier prepared in Example 1.

[0032] Figure 3 shows the SEM image of the outer surface of the alumina support prepared in Comparative Example 2.

[0033] Figure 4 The image shows a cross-sectional SEM image of the alumina support prepared in Comparative Example 2. Detailed Implementation

[0034] 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.

[0035] 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.

[0036] The micro-region composition of the sample was characterized using scanning electron microscopy-energy dispersive spectroscopy (SEM-EDAX). The specific procedures were as follows: A JSM-7500F SEM equipped with an EDAX spectrometer was used, with an accelerating voltage of 30 kV, a probe current of 11 µA, and a working distance of 8 mm. During the measurement, catalyst particles were cut and adhered to the SEM stage, ensuring the cross-section of the catalyst particles was perpendicular to the electron beam direction of the SEM. Twenty granular particle micro-regions and spherical cavity micro-regions were selected as measurement areas. The contents of molybdenum oxide and nickel oxide in the corresponding areas were measured, and the average values ​​were taken.

[0037] The catalyst bulk phase molybdenum-nickel content is determined according to the method of ICP-AES determination of metal element content in molybdenum-nickel series hydrogenation catalyst in Guangzhou Chemical Industry, 2021, 49, (17): 129-130.

[0038] Preparation of microspherical activated carbon:

[0039] The microspherical activated carbon used in the method of the application is prepared according to the method of Lin DL, Li W, Wu J, et al. Preparation of microspherical activated carbon by hydrothermal carbonization-CO2 activation of carboxymethylcellulose [J]. Wood Chemistry and Industry, 2015, 35 (4): 21-27. The prepared microspherical activated carbon has a diameter of 1-5 microns and 5-10 microns. Example 1

[0040] 32 grams of methylcellulose are mixed uniformly with 200 grams of pseudoboehmite (pore size 10 nm),

[0041] The mixed material is placed in a rotary table forming machine and mixed uniformly, the inclination angle of the rotary table is adjusted to 45°, and the rotary speed of the rotary table is 15 rpm; a 1% acetic acid aqueous solution is sprayed onto the material in the rotary table by a sprayer, and after mixing and contacting, the material is formed in the rotary table for 25 min to obtain a spherical precursor S0;

[0042] (2) 20 grams of microspherical activated carbon with a diameter of 1-5 microns are taken, impregnated with an aluminum nitrate solution with a concentration of 16.5 wt% to make the activated carbon adsorb and saturate, and the adsorbed material is dried at 80°C for 4 hours; then the microspherical activated carbon is impregnated with a Mo-Ni-P solution with a molybdenum oxide concentration of 2.1 g / 100 mL and a nickel oxide concentration of 0.5 g / 100 mL to make it adsorb and saturate, and the adsorbed material is dried at 80°C for 4 hours. The dried microspherical activated carbon is mixed uniformly with 200 grams of pseudoboehmite (pore size 15 nm), and the mixed material and the spherical precursor S0 prepared in step (1) are placed in a rotary table forming machine and mixed uniformly, the inclination angle of the rotary table is adjusted to 45°, and the rotary speed of the rotary table is 15 rpm; a 1% acetic acid aqueous solution is sprayed onto the material in the rotary table by a sprayer, and after mixing and contacting, the material is formed in the rotary table for 25 min to obtain a spherical precursor S1;

[0043] (3) Take 29 grams of activated carbon with a diameter of 5-10 microns, immerse it in an aluminum nitrate solution with a concentration of 27.5 wt% to make the activated carbon adsorb saturated, and dry the adsorbed material at 80°C for 4 hours; then immerse the spherical activated carbon in a Mo-Ni-P solution with a molybdenum oxide concentration of 4.2 g / 100 mL and a nickel oxide concentration of 1.1 g / 100 mL to make it adsorb saturated, and dry the adsorbed material at 80°C for 4 hours. Mix the above dried micron spherical activated carbon with 200 grams of pseudoboehmite (pore size 17.5 nm) uniformly, mix the mixed material and the spherical precursor S1 prepared in step (2) in a rotary table forming machine, adjust the inclination angle of the rotary table to 45°, and the rotation speed of the rotary table to 15 rpm, spray 1% acetic acid aqueous solution with a mass concentration of 1% through a sprayer onto the material in the rotary table, after mixing and contacting, the material is shaped in the rotary table for 20 min, to obtain spherical precursor S2. Dry the obtained spherical precursor S2 at 140°C for 6h, and calcine it at 550°C in an oxygen atmosphere for 6h to obtain an alumina carrier precursor.

[0044] (4) Take 100 grams of the alumina carrier precursor of step (3), add 580 grams of propylene oxide aqueous solution with a mass concentration of 6.6%, and mix the material into an autoclave, seal the autoclave in an oven, first seal it at 80°C for 3 hours, then heat it to 140°C for 17.5 hours of sealed treatment, and after cooling, wash and filter the material, dry the solid material at 140°C for 6 hours, and calcine it at 650°C in an air atmosphere for 6 hours to prepare an alumina carrier A1, the properties of which are shown in Table 1, the outer surface scanning electron microscope image of the carrier is shown in Figure 1 , and the cross-sectional scanning electron microscope image is shown in Figure 2 .

[0045] (5) Take 100 grams of the alumina carrier of step (4) and place it in a spray-impregnation rolling pot, and use a saturated impregnation method to spray-impregnate the alumina carrier with an active component impregnating solution with a molybdenum oxide concentration of 9.3 g / 100 mL and a nickel oxide concentration of 2.4 g / 100 mL, dry the impregnated material at 120°C for 4 hours, and calcine it at 500°C for 5 hours to prepare the hydrogen demetallization catalyst Cat-1 of the present application, the properties of which are shown in Table 1. Example 2

[0046] The same as example 1, except that the methyl cellulose is added in step (1) in an amount of 28 grams; the aluminum nitrate solution concentration is 10.5 wt% in step (2), the Mo-Ni-P solution has a molybdenum oxide concentration of 1.8 g / 100 mL and a nickel oxide concentration of 0.5 g / 100 mL, and the microspherical activated carbon is added in an amount of 23 grams; the aluminum nitrate solution concentration is 29 wt% in step (3), the Mo-Ni-P solution has a molybdenum oxide concentration of 4.4 g / 100 mL and a nickel oxide concentration of 1.2 g / 100 mL, and the microspherical activated carbon is added in an amount of 33 grams. The propylene oxide concentration is 5.2% in step (4), and the solution amount is 660 grams. During the hydrothermal treatment, the temperature is first raised to 90°C and maintained for 2 hours, and then raised to 150°C and maintained for 16.5 hours. The hydrogen demetallization catalyst Cat-2 of the present application is prepared, and the catalyst properties are shown in Table 1. Example 3

[0047] The same as example 1, except that the methyl cellulose is added in step (1) in an amount of 36 grams; the aluminum nitrate solution concentration is 13.5 wt% in step (2), the Mo-Ni-P solution has a molybdenum oxide concentration of 2.5 g / 100 mL and a nickel oxide concentration of 0.6 g / 100 mL, and the microspherical activated carbon is added in an amount of 18 grams; the aluminum nitrate solution concentration is 25 wt% in step (3), the Mo-Ni-P solution has a molybdenum oxide concentration of 3.9 g / 100 mL and a nickel oxide concentration of 1.0 g / 100 mL, and the microspherical activated carbon is added in an amount of 38 grams. The propylene oxide concentration is 7.4% in step (4), and the solution amount is 480 grams. During the hydrothermal treatment, the temperature is first raised to 70°C and maintained for 3.5 hours, and then raised to 130°C and maintained for 18.5 hours. The hydrogen demetallization catalyst Cat-3 of the present application is prepared, and the catalyst properties are shown in Table 1. Example 4

[0048] The same as example 1, except that the methyl cellulose is added in step (1) in an amount of 24 grams; the aluminum nitrate solution concentration is 19.5 wt% in step (2), the Mo-Ni-P solution has a molybdenum oxide concentration of 2.8 g / 100 mL and a nickel oxide concentration of 0.7 g / 100 mL, and the microspherical activated carbon is added in an amount of 26 grams; the aluminum nitrate solution concentration is 22.5 wt% in step (3), the Mo-Ni-P solution has a molybdenum oxide concentration of 3.5 g / 100 mL and a nickel oxide concentration of 0.9 g / 100 mL, and the microspherical activated carbon is added in an amount of 25 grams. The propylene oxide concentration is 4.6% in step (4), and the solution amount is 710 grams. During the hydrothermal treatment, the temperature is first raised to 100°C and maintained for 1.5 hours, and then raised to 160°C and maintained for 15.5 hours. The hydrogen demetallization catalyst Cat-4 of the present application is prepared, and the catalyst properties are shown in Table 1.

[0049] Comparative Example 1

[0050] The same as Example 1, except that the propylene oxide aqueous solution in step (4) is replaced by an aqueous ammonia solution of the same mass concentration, to prepare a comparative hydrogen demetallization catalyst Cat-5, the catalyst properties are shown in Table 1.

[0051] Comparative Example 2

[0052] The same as Example 1, except that the propylene oxide aqueous solution in step (4) is replaced by an ethylene oxide solution of the same concentration, to prepare a comparative hydrogen demetallization catalyst Cat-6, the catalyst properties are shown in Table 1, the corresponding carrier and the precursor of the carrier in Example 1 have a similar morphology, and no flaky structure is observed, and the specific scanning electron microscope image is shown in Figure 3 , and the cross-sectional scanning electron microscope image is shown in Figure 4 .

[0053] Comparative Example 3

[0054] The same as Example 1, except that the propylene oxide concentration in step (4) is 1%, to prepare a comparative hydrogen demetallization catalyst Cat-7, the catalyst properties are shown in Table 1.

[0055] Comparative Example 4

[0056] The same as Example 1, except that the micron spherical activated carbon in step (2) and step (3) is not impregnated with an active metal component, but the active metal component is loaded onto the carrier for the first time in step (5), to prepare a comparative hydrogen demetallization catalyst Cat-8 with the same active metal content, the catalyst properties are shown in Table 1.

[0057] Table 1 Catalyst properties

[0058]

[0059] From the data in Table 1 and Figures 1-4 It can be seen that, compared with the comparative examples, the hydrogen demetallization catalyst prepared by the method of the present application has a high content of large pores on the surface, the pore is wide, and a large number of 50-100 nm pores are formed by the accumulation of flaky particles in the micron-level spherical cavities inside the catalyst, and the content of the active metal component in the catalyst matches well with the pores of the catalyst. Example

[0060] The hydrogen demetallization catalysts Cat-1 to Cat-4 prepared by the present application and the hydrogen demetallization catalysts Cat-5 to Cat-8 prepared by the comparative examples are respectively filled into a fixed bed hydrogenation reactor, the raw materials (see Table 2) are treated, and the test conditions are as follows: reaction temperature 375°C, hydrogen / oil volume ratio 700, liquid hourly space velocity 0.8h -1 , hydrogen partial pressure 14.5 MPa, continuous operation for 2000 hours, and the impurity removal properties are shown in Table 3.

[0061] Table 2 Raw material properties

[0062]

[0063] Table 3 Evaluation results of catalysts

[0064] Hydrogenation guard catalyst Cat-1 Cat-2 Cat-3 Cat-4 Cat-5 Cat-6 Cat-7 Cat-8 Relative Ni+V removal, % 131 126 129 127 100 103 98 120 Relative S removal, % 126 129 124 125 100 99 105 115

[0065] From the results in Table 3, it can be seen that the hydrogenation demetallization catalyst prepared by the method of the present application has higher demetallization Ni, V activity, higher desulfurization activity and better activity stability.

Claims

1. A method for preparing a heavy oil hydroprocessing catalyst, comprising the following steps: (1) mixing pseudo-boehmite P1 and a physical pore-expanding agent uniformly, and rolling to form a spherical precursor S0; (2) mixing pseudo-boehmite P2, microspherical activated carbon Q1 impregnated with an appropriate amount of aluminum nitrate solution A and active metal component solution I uniformly to obtain material W1, and mixing the material W1 with the spherical precursor S0, and rolling to form a spherical precursor S1; (3) mixing pseudo-boehmite P3, microspherical activated carbon Q2 impregnated with an appropriate amount of aluminum nitrate solution B and active metal component solution II uniformly to obtain material W2, and mixing the material W2 with the spherical precursor S1, and rolling, and then drying and calcining to obtain a precursor S2; (4) sealing and heat-treating the precursor S2 of step (3) in an aqueous propylene oxide solution, and after treatment, the material is subjected to solid-liquid separation, and the solid material is dried and calcined to obtain an alumina carrier, and then loaded with a hydrogenation active component to obtain a catalyst product; in step (2), the concentration of the aluminum nitrate solution A is 10wt%-20wt%, and the solution amount is such that the microspherical activated carbon is saturated with adsorption; in step (2), the active metal component solution I is a solution containing molybdenum and nickel, the molybdenum concentration in the solution is 1.5-3g / 100mL as molybdenum trioxide, and the nickel concentration in the solution is 0.4-1g / 100mL as nickel oxide, and the solution amount is such that the microspherical activated carbon is saturated with adsorption; in step (3), the concentration of the aluminum nitrate solution B is 20wt%-30wt%, and the solution amount is such that the microspherical activated carbon is saturated with adsorption; in step (3), the active metal component solution II is a solution containing molybdenum and nickel, the molybdenum concentration in the solution is 3-4.5g / 100mL as molybdenum trioxide, and the nickel concentration in the solution is 0.8-1.2g / 100mL as nickel oxide, and the solution amount is such that the microspherical activated carbon is saturated with adsorption; in step (4), the aqueous propylene oxide solution has a mass percentage concentration of 2.5%-12%; the mass ratio of the aqueous propylene oxide solution to the alumina carrier precursor is 3:1-10:1; in step (4), the sealing and heat-treatment process comprises the following steps: first, low-temperature sealing and heat-treatment at 60-100℃ for 1-4 hours, and then sealing and heat-treatment at 110-180℃ for 14-20 hours.

2. The method of claim 1, wherein: In step (1), the pseudo-boehmite P1 has a particle morphology of granules, and the pore size is 8.5-10nm.

3. The method of claim 1, wherein: In step (1), the physical pore-expanding agent is one or more of activated carbon, wood chips, carbon black, urea, propylene glycol glycerol, triethylene glycol, melamine, polyethylene glycol, polyethylene oxide, methyl cellulose, polyethylene oxide, polyacrylamide and starch; the mass ratio of the physical pore-expanding agent to the pseudo-boehmite P1 is 1:20-1:

10.

4. The method of claim 1, wherein: In step (1), the radius of the spherical precursor S0 is 0.2r-0.6r, and the radius of the spherical precursor S1 is 0.5r-0.8r, where r is the radius of the alumina carrier, i.e. the straight-line distance from the center of the sphere to the outer surface.

5. The method of claim 1, wherein: The pseudo-boehmite P2 particle morphology is granular, and the average pore diameter is 10-15 nm; the diameter of the microspherical activated carbon Q1 is 1-5 microns, and the mass ratio of the microspherical activated carbon to the pseudo-boehmite P2 is 1:6.7-1:12.

5.

6. The method of claim 1, wherein: The pseudo-boehmite P3 particle morphology is granular, and the average pore diameter is greater than 15 nm.

7. The method of claim 1, wherein: The diameter of the microspherical activated carbon Q2 is 5-10 microns, and the mass ratio of the microspherical activated carbon to the pseudo-boehmite P3 is 1:5-1:

10.

8. The method of claim 1, wherein: The drying temperature of step (3) is 100-160℃, and the drying time is 2-8 hours; the calcination is carried out under an oxygen atmosphere, the calcination temperature is 450-600℃, and the calcination time is 4-8 hours.

9. The method of claim 1, wherein: The loading mode of step (4) is impregnation, and the Mo content in the impregnation solution of the hydrogenation active component is 7.5%-13.5g / 100mL as metal oxide, and the Ni content is 2.1-4.5g / 100mL as metal oxide.

10. The method of claim 1, wherein: The drying temperature of step (4) is 100-160℃, 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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