A fluidized bed heavy oil hydrotreating catalyst, its preparation method and application

Abstract

The present invention discloses an ebullated bed heavy oil hydrogenation catalyst and its preparation method and application. The ebullated bed heavy oil hydrogenation catalyst comprises an active metal component, an auxiliary active metal component, an optional auxiliary agent and a carrier. The preparation method comprises the following steps: (1) forming pseudo-boehmite powder into balls to obtain a carrier precursor A; (2) mixing an organic polymer A, a nitrogen-containing weak base compound and pseudo-boehmite powder to obtain a mixed material; (3) preparing a carrier precursor B by combining the carrier precursor A with the mixed material and an aqueous solution of the organic polymer B after heat treatment; (4) heat-treating the carrier precursor B at a low temperature to obtain a carrier precursor C; (5) mixing the carrier precursor C with a soluble zirconium salt solution, drying it and calcining it under an inert atmosphere to obtain a carrier; (6) introducing the active metal component onto the carrier, drying it and calcining it to obtain a hydrogenation catalyst. The catalyst of the present invention not only has high hydrogenation demetallization activity and the ability to tolerate impurities such as metals, but also can ensure the stability of the catalyst during long-term operation of the device.

Description

Technical Field

[0001] The invention belongs to the technical field of oil refining and chemical industry, and relates to a hydrogenation catalyst and a preparation method thereof, in particular to a fluidized bed heavy oil hydrogenation catalyst and a preparation method thereof. Background Art

[0002] In recent years, with the deterioration of crude oil quality, the development of deep processing of heavy oil and the increase of product value have become of great practical significance. Ebullating bed hydrogenation technology has seen rapid development in recent years. It can use low-quality, low-cost heavy oil as a raw material, resulting in lower production costs and significant economic benefits. Because the ebullating bed can add and remove catalysts online, it consumes a large amount of catalyst during operation, placing higher demands on catalyst performance and cost. The reaction performance of hydrogenation catalysts depends not only on the inherent catalytic properties of the active components but also on the properties of the catalyst support. The specific surface area, pore structure, and surface acidity of the support have a significant impact on the dispersion of the active components, the interaction between the active components and the support, the diffusion of reactant molecules, and the catalyst's resistance to poisoning. Currently, the most widely used support in heavy oil hydrogenation is alumina. While it has excellent mechanical properties and a low price, it also has disadvantages such as a low specific surface area and strong interaction with active metals. Consequently, researchers have conducted extensive research on alumina modification.

[0003] CN201810893969.4 discloses a method for preparing an ebullated bed hydroprocessing catalyst. The method comprises the following steps: (1) kneading pseudo-boehmite with basic aluminum ammonium carbonate containing a carbon precursor solution into a molded product, and drying the molded product; (2) spraying the material obtained in step (1) with a carbon precursor solution, drying and calcining the sprayed material to produce an alumina support; and (3) impregnating the alumina support obtained in step (2) with an impregnation solution containing a hydrogenation active component, drying and calcining the impregnation product to produce the ebullated bed hydroprocessing catalyst. The catalyst prepared by the method of the present invention has high strength and wear resistance and is particularly suitable for heavy oil ebullated bed hydroprocessing processes. However, the carbon precursor has a weak pore-expanding effect, and the alumina support has a strong interaction with the active metal, resulting in a low utilization rate.

[0004] US4448896 discloses a catalyst for hydrodesulfurization and demetallization, wherein the catalyst is prepared by loading the active component onto a catalyst having a specific surface area of 100 to 350 m 2 / g, an alumina support with a pore radius of 3.75-7500nm and a pore volume of 0.5-1.5mL / g. The support is prepared by mixing activated alumina or an activated alumina precursor with carbon black, forming, and calcining. The patent uses carbon black for pore expansion. Although this increases the support's pore volume, its effect on macropore expansion is limited, and the catalyst's metal-carrying capacity needs to be improved. Summary of the Invention

[0005] To overcome the shortcomings of the prior art, the present invention primarily provides an ebullated-bed heavy oil hydrogenation catalyst, its preparation method, and its application. The catalyst exhibits a nonuniform pore distribution and a nonuniform distribution of active metals, making it particularly suitable for heavy oil and residual oil hydroprocessing. The catalyst exhibits high hydrodemetallization activity and tolerance to metal and other impurities, as well as high desulfurization activity. Furthermore, the catalyst is less susceptible to clogging by metal and other impurities, ensuring catalyst stability during long-term operation of the device.

[0006] A first aspect of the present invention provides a method for preparing an ebullated-bed heavy oil hydrogenation catalyst, comprising the following steps:

[0007] (1) Pseudo-boehmite powder is spherical-molded to obtain a carrier precursor A;

[0008] (2) mixing the organic high molecular polymer A, the nitrogen-containing weak base compound, and the pseudo-boehmite powder to obtain a mixed material;

[0009] (3) placing the carrier precursor A obtained in step (1) into a ball rolling machine, and uniformly adding the mixed material obtained in step (2) and the aqueous solution of the heat-treated organic high molecular polymer B during the rolling process to obtain a carrier precursor B;

[0010] (4) subjecting the carrier precursor B obtained in step (3) to low-temperature heat treatment to obtain a carrier precursor C;

[0011] (5) mixing the carrier precursor C obtained in step (4) with a soluble zirconium salt solution, drying the mixture, and calcining the mixture under an inert atmosphere to obtain a carrier;

[0012] (6) An active metal component is introduced into the carrier obtained in step (5), followed by drying and calcination to obtain a hydrogenation catalyst.

[0013] Furthermore, in the above-mentioned preparation method of the ebullating bed heavy oil hydrogenation catalyst, the pseudo-boehmite powder in step (1) and step (2) can be a commercially available product or a pseudo-boehmite powder prepared according to an existing method.

[0014] Furthermore, in the above-mentioned method for preparing the ebullated bed heavy oil hydrogenation catalyst, the pseudo-boehmite powder in step (1) and step (2) can be pseudo-boehmite powder of the same properties or pseudo-boehmite powder of different properties.

[0015] Furthermore, in the preparation method of the above-mentioned ebullated bed heavy oil hydrogenation catalyst, the spherical molding described in step (1) can adopt any of the existing spherical molding methods in the art, specifically one or more of the extrusion spherical molding, rolling molding, and spray drying molding methods.

[0016] Furthermore, in the above-mentioned method for preparing the ebullating bed heavy oil hydrogenation catalyst, the particle size of the carrier precursor A in step (1) is 0.1 to 1.0 mm, preferably 0.3 to 0.7 mm.

[0017] Furthermore, in the above-mentioned method for preparing the ebullating bed heavy oil hydrogenation catalyst, the organic high molecular polymer A in step (2) is one or more of starch, cellulose ether, sugar, and flour, preferably starch. More specifically, the starch is one or more of mung bean starch, cassava starch, sweet potato starch, potato starch, wheat starch, water chestnut starch, lotus root starch, and corn starch, preferably corn starch and / or potato starch; the cellulose ether can be at least one of methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose, preferably methyl cellulose; and the saccharide is one or more of monosaccharides, disaccharides, and polysaccharides, preferably glucose.

[0018] Furthermore, in the above-mentioned method for preparing an ebullating-bed heavy oil hydrogenation catalyst, the nitrogen-containing weak base compound in step (2) is one or a mixture of two or more of ammonia water, ammonium carbonate, and ammonium bicarbonate, preferably ammonia water. Furthermore, the concentration of the aqueous solution of the nitrogen-containing weak base compound is 2 wt% to 40 wt%, preferably 5 wt% to 30 wt%.

[0019] Furthermore, in the above-mentioned preparation method of the ebullating bed heavy oil hydrogenation catalyst, the mass ratio of the organic high molecular polymer A and the nitrogen-containing weak base compound aqueous solution in step (2) is 1:0.05 to 1:0.5.

[0020] Furthermore, in the above-mentioned preparation method of the ebullating bed heavy oil hydrogenation catalyst, the amount of the organic high molecular polymer A and the nitrogen-containing weak base compound added in step (2) (by mass) is 5wt% to 40wt% of the dry mass of the pseudo-boehmite powder, preferably 10wt% to 30wt%.

[0021] Furthermore, in the above-mentioned preparation method of the ebullated bed heavy oil hydrogenation catalyst, when the organic high molecular polymer A, the nitrogen-containing weak base compound, and the pseudo-boehmite powder are mixed in step (2), it is preferred that the organic high molecular polymer A and the nitrogen-containing weak base compound are first mixed, and then mixed with the pseudo-boehmite powder.

[0022] Furthermore, in the above-mentioned method for preparing an ebullating-bed heavy oil hydrogenation catalyst, the concentration of the aqueous solution of the heat-treated organic polymer B in step (3) is 0.5 wt% to 8 wt%, preferably 1 wt% to 5 wt%. The preparation method is as follows: adding the organic polymer B to water, heating and mixing at 60 to 100° C. for 10 to 40 minutes, and obtaining the aqueous solution of the heat-treated organic polymer B after the organic polymer B is completely dissolved.

[0023] Furthermore, in the above-mentioned preparation method of the ebullating bed heavy oil hydrogenation catalyst, the mass ratio of the added amount of the aqueous solution of the heat-treated organic high molecular polymer B to the mixed material in step (3) is 0.5 to 1.5.

[0024] Furthermore, in the above-mentioned method for preparing the ebullating bed heavy oil hydrogenation catalyst, the organic high molecular polymer B in step (3) is one or more of starch, sugar, cellulose ether, and flour, preferably starch. Furthermore, the starch is one or more of mung bean starch, cassava starch, sweet potato starch, potato starch, wheat starch, water chestnut starch, lotus root starch, and corn starch, preferably corn starch and / or potato starch; the cellulose ether can be at least one of methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose, preferably methyl cellulose; the saccharide is one or more of monosaccharide, disaccharide, and polysaccharide, preferably glucose.

[0025] Furthermore, in the preparation method of the above-mentioned ebullated bed heavy oil hydrogenation catalyst, the low-temperature heat treatment temperature in step (4) is 100-300°C, preferably 150-250°C; and the treatment time is 3-12h.

[0026] Furthermore, in the above-mentioned preparation method of the ebullating bed heavy oil hydrogenation catalyst, the soluble zirconium salt described in step (5) is one or more of zirconium nitrate, zirconium chloride, zirconium sulfate, etc.

[0027] Furthermore, in the above-mentioned method for preparing the ebullating bed heavy oil hydrogenation catalyst, the drying temperature in step (5) is 60-120°C.

[0028] Furthermore, in the preparation method of the above-mentioned ebullated bed heavy oil hydrogenation catalyst, the calcination under an inert atmosphere in step (5) is performed, and the inert atmosphere is one or more of nitrogen, helium, neon, argon, krypton, and xenon, preferably nitrogen; the calcination temperature is 600-900°C, and the calcination time is 1-5 hours.

[0029] Furthermore, in the above-mentioned method for preparing the ebullating bed heavy oil hydrogenation catalyst, the particle size of the carrier in step (5) is 0.2 to 2.0 mm, preferably 0.3 to 1.8 mm.

[0030] Furthermore, in the preparation method of the above-mentioned ebullated bed heavy oil hydrogenation catalyst, the introduction of the active metal component described in step (6) can adopt any one or more of the existing methods in the art, specifically at least one of the kneading, impregnation and other methods, preferably the impregnation method.

[0031] Furthermore, in the above-mentioned preparation method of the ebullating bed heavy oil hydrogenation catalyst, the active metal component described in step (6) is one or more of Group VIB metals and / or Group VIII metals, wherein the Group VIB metals are generally Mo and / or W, and the Group VIII metals are generally Ni and / or Co.

[0032] Furthermore, in the above-mentioned method for preparing the ebullating bed heavy oil hydrogenation catalyst, the active metal components described in step (6) are preferably Mo and Ni.

[0033] Furthermore, in the above-mentioned preparation method of the ebullating bed heavy oil hydrogenation catalyst, when introducing the active metal component in step (6), an auxiliary agent P may also be introduced.

[0034] Furthermore, in the above-mentioned preparation method of the ebullated bed heavy oil hydrogenation catalyst, the drying in step (6) is performed at 80 to 120° C. for 4 to 12 hours.

[0035] Furthermore, in the preparation method of the ebullating bed heavy oil hydrogenation catalyst, the calcination temperature in step (6) is 400-600°C, and the calcination time is 1-5 hours. The calcination is carried out in the presence of an oxygen-containing atmosphere, such as air.

[0036] Furthermore, in the above-mentioned method for preparing the ebullating bed heavy oil hydrogenation catalyst, when the active metal component described in step (6) is prepared by an impregnation method, a precursor containing the active metal component, water, and an optional phosphorus-containing compound are first mixed uniformly to obtain an aqueous solution containing the hydrogenation metal component and P. The aqueous solution is then mixed uniformly with the carrier, allowed to stand, dried, and calcined to obtain the catalyst. Specifically, the precursor containing the active metal component is a compound containing a Group VIB metal and / or a Group VIII metal. The Group VIB metal-containing compound can be one or more of a molybdenum-containing compound and a tungsten-containing compound. The Group VIII metal-containing compound can be one or more of a nickel-containing compound and a cobalt-containing compound. The molybdenum-containing compound can be molybdenum oxide and / or ammonium heptamolybdate; the nickel-containing compound can be basic nickel carbonate and / or nickel nitrate; and the cobalt-containing compound can be basic cobalt carbonate and / or cobalt nitrate. The phosphorus-containing compound may be one or more of phosphoric acid, ammonium dihydrogen phosphate, and ammonium monohydrogen phosphate. The concentration of the hydrogenation metal component in the aqueous solution containing the hydrogenation metal component and P is 0.03 to 0.5 g / mL (calculated as hydrogenation metal oxide), and the concentration of P is 0 to 0.05 g / mL, preferably 0.002 to 0.05 g / mL. The standing time is 1 to 3 hours.

[0037] The second aspect of the present invention provides an ebullated bed heavy oil hydrogenation catalyst obtained by the above preparation method.

[0038] Furthermore, in the above-mentioned ebullated bed heavy oil hydrogenation catalyst, the ebullated bed heavy oil hydrogenation catalyst includes an active metal component, a promoter metal component, optional phosphorus pentoxide and a carrier, the active metal is one or more of Group VIB metals and / or Group VIII metals, the promoter metal is zirconium, and the carrier is alumina, wherein the active metal and the promoter metal are present on the carrier in the form of oxides.

[0039] Furthermore, in the above-mentioned ebullated-bed heavy oil hydrogenation catalyst, based on the weight of the catalyst and calculated as oxide, the content of the metal component of Group VIB is 2wt% to 15wt%; the content of the metal component of Group VIII is 0.5wt% to 5wt%; the content of the promoter metal component is 0.1wt% to 2wt%; and the content of phosphorus pentoxide is 0.4wt% to 4wt%.

[0040] Furthermore, in the above-mentioned ebullated-bed heavy oil hydrogenation catalyst, the Group VIB metal is generally Mo and / or W, and the Group VIII metal is generally Ni and / or Co.

[0041] Furthermore, in the above-mentioned ebullated-bed heavy oil hydrogenation catalyst, the metal components are more preferably Mo and Ni.

[0042] Furthermore, in the above-mentioned ebullated bed heavy oil hydrogenation catalyst, the properties of the ebullated bed heavy oil hydrogenation catalyst are as follows: the specific surface area is 120 to 250 m 2 / g, the pore volume is 0.60-0.90 mL / g, and the pore volume of pores with a pore diameter greater than 50 nm accounts for more than 3% of the total pore volume, preferably 5%-15%.

[0043] Furthermore, in the above-mentioned ebullated bed heavy oil hydrogenation catalyst, the active metal of the ebullated bed heavy oil hydrogenation catalyst is distributed relatively less on the outside and relatively more on the inside, showing an uneven distribution.

[0044] A third aspect of the present invention provides a use of the above-mentioned ebullated-bed heavy oil hydrogenation catalyst in a heavy oil hydrogenation process.

[0045] Furthermore, in the application of the above-mentioned ebullated bed heavy oil hydrogenation catalyst in the heavy oil hydrogenation process, the heavy oil is at least one or more of atmospheric residue oil, vacuum residue oil, catalytic slurry oil, and coal tar.

[0046] Furthermore, in the application of the ebullated bed heavy oil hydrogenation catalyst in the heavy oil hydrogenation process, the hydrogenation process process conditions are as follows: reaction pressure of 10-20 MPa, temperature of 300-500°C, liquid hourly volume space velocity of 0.1-1.5h -1 , the hydrogen-to-oil volume ratio is 300-1000.

[0047] Compared with the prior art, the ebullated bed heavy oil hydrogenation catalyst and its preparation method provided by the present invention have the following advantages:

[0048] 1. In the preparation method of the ebullated-bed heavy oil hydrogenation catalyst of the present invention, the organic high molecular weight polymer A is reacted with a weak base compound and then mixed with pseudo-boehmite powder, which only has a pore-expanding effect and has poor adhesion. However, the organic high molecular weight polymer B, after heat treatment, decomposes into small molecules in water, making the aqueous solution highly adhesive and enabling a strong interaction between the mixture A and the carrier precursor A. This can enhance the interaction between the pseudo-boehmite powder, that is, enhance the interaction between the carrier alumina and the carrier, thereby improving the strength and wear resistance of the carrier.

[0049] 2. In the preparation method of the ebullating bed heavy oil hydrogenation catalyst of the present invention, the carrier precursor B is treated at low temperature, and the ammonia in the nitrogen-containing weak base compound that reacts with the organic high molecular polymer A will volatilize, interact with the strong acid sites on the alumina, and be adsorbed. The addition of a soluble zirconium salt will interact with the ammonia on the alumina and adsorb on the strong acid sites of the alumina. After calcination, it will occupy the strong acid sites of the alumina, which can weaken the interaction between the active metal and the carrier alumina and improve the utilization rate of the active metal.

[0050] 3. In the preparation method of the ebullated-bed heavy oil hydrogenation catalyst of the present invention, organic polymer A is calcined under an inert atmosphere or nitrogen atmosphere to form a macroporous carbon material, while organic polymer B, which has been decomposed into small molecules, is calcined under an inert atmosphere or nitrogen atmosphere to form a microporous carbon material. The macroporous carbon material expands the pores of the outer alumina layer, while the microporous carbon material improves the structural stability of the outer alumina layer and enhances the support strength. Because the macroporous carbon material has a lower water absorption rate than alumina and the microporous carbon material partially blocks the pores of the outer alumina layer, the presence of the carbon material reduces the water absorption rate of the outer alumina support. During the active metal impregnation process, the outer layer of the support absorbs relatively less active metal, while the inner alumina layer absorbs relatively more active metal. The resulting catalyst exhibits an uneven distribution of active metal, with more active metal distributed inside the catalyst and less distributed outside. The catalyst activity is then graded, allowing for uniform deposition of metal impurities on the catalyst and preventing clogging of the catalyst's outer pores, thereby improving active metal utilization and enhancing catalyst stability.

[0051] 4. In the preparation method of the ebullated bed heavy oil hydrogenation catalyst of the present invention, the macroporous carbon material generated by the organic high molecular polymer A on the carrier alumina is completely burned during the catalyst calcination process, thereby increasing the number of macropores in the outer layer of the alumina carrier and expanding the pores of the outer layer of the alumina carrier. This gives the catalyst an uneven pore distribution and is not easily clogged by impurities such as metals. This solves the problem of mismatch between the hydrodemetallization activity, hydrodesulfurization activity and the capacity to tolerate impurities such as metals in existing hydrogenation catalysts, and can ensure the stability of the catalyst during long-term operation of the device. The catalyst is particularly suitable for the hydrogenation of heavy oil and residual oil. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 Electron probe point diagram of the catalyst cross section.

[0053] Figure 2 The electron probe scan shows the MoO3 distribution on the catalyst cross section. DETAILED DESCRIPTION

[0054] The technical solutions and effects of the present invention are further illustrated below by specific examples. In the present invention, wt% refers to mass fraction.

[0055] In the present invention, the wear index of microsphere carriers <0.8 mm is tested by high-speed air jet method (see ASTM D5757-00), and the wear index of microsphere carriers >0.8 mm is measured by drum method using KM-ZV abraser; the lateral pressure strength is measured using ZQJ-II intelligent particle strength testing machine.

[0056] The specific surface area and pore volume in this invention are measured using a low-temperature liquid nitrogen physical adsorption method, specifically a US Micromeritics ASAP2420 low-temperature nitrogen adsorption instrument. The specific process involves vacuum treating a small amount of sample at 300°C for 3-4 hours, followed by nitrogen adsorption-desorption testing in liquid nitrogen at -200°C. The surface area is calculated using the BET equation, and the pore size distribution is derived using the BJH model.

[0057] The distribution of active metals in the catalyst was detected using a JXA-8230 electron probe microanalyzer from JEOL Ltd.

[0058] Example 1

[0059] (1) Vector preparation

[0060] Pseudo-boehmite powder (specific surface area 308m 2 / g, pore volume 1.02mL / g) was rolled in a ball mill to produce spherical carrier precursor A with a diameter of 0.4-0.5mm. 31.5g of corn starch was mixed with 30g of 10wt% ammonia water and then mixed with 300g of pseudo-boehmite powder to obtain a mixture. 3.5g of corn starch was added to 100g of water and heated at 70°C for 20min to obtain an aqueous solution of organic polymer B. 100g of carrier precursor A was placed in a ball mill and evenly sprinkled with the mixture and the aqueous solution of organic polymer B during rolling. The ball mill was rotated at 30 rpm. After balling, carrier precursor B with a diameter of 0.6-0.7mm was obtained. Carrier precursor B was subjected to low-temperature heat treatment at 200°C for 4h to obtain carrier precursor C. 50 mL of an aqueous solution containing 4.93 g of zirconium nitrate was added to 100 g of carrier precursor C, dried at 90°C for 8 h, and then calcined at 750°C for 3 h under a nitrogen atmosphere to obtain a spherical carrier with a particle size of 0.6-0.7 mm. The carrier yield and attrition data are shown in Table 1.

[0061] (2) Catalyst preparation

[0062] Dissolve 1.57 g of phosphoric acid H3PO4 (concentration 85 wt%) in 50 mL of water, then add 4.27 g of molybdenum trioxide and 1.88 g of basic nickel carbonate, heat to 100 ° C and stir under reflux for 2.0 h, filter and adjust the volume to 85 mL to obtain a Mo-Ni-P aqueous solution.

[0063] The Mo-Ni-P aqueous solution was added to 100 g of the prepared support, mixed thoroughly, and allowed to stand for 3 hours. The mixture was then dried at 110°C for 4 hours and calcined at 550°C for 3 hours to obtain a catalyst with a MoO3 content of 4.0 wt%, a NiO content of 1.0 wt%, and a P content of 0.4 wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0064] (3) Catalyst evaluation

[0065] The catalyst activity was evaluated over a long period using a pilot hydrogenation unit with a run time of 1500 h. The catalyst evaluation conditions were: reaction temperature 420°C, reaction pressure 15.0 MPa, and volume space velocity 0.3 h-1. -1 The hydrogen-to-oil volume ratio was 500:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0066] Example 2

[0067] (1) Vector preparation

[0068] Pseudo-boehmite powder (specific surface area 308m 2 / g, pore volume 1.02 mL / g) was rolled in a ball mill to produce spherical carrier precursor A with a diameter of 0.4-0.5 mm. 42.0 g of corn starch was mixed with 50 g of a 15 wt% aqueous ammonium carbonate solution and then mixed with 300 g of pseudo-boehmite powder to produce a mixture. 3.5 g of corn starch was added to 100 g of water and heated at 70°C for 20 minutes to produce an aqueous solution of organic polymer B. 100 g of carrier precursor A was placed in a ball mill and evenly sprinkled with the mixture and the aqueous solution of organic polymer B during rolling. The ball mill was rotated at 30 rpm. After balling, carrier precursor B with a diameter of 0.6-0.7 mm was produced. Carrier precursor B was subjected to a low-temperature heat treatment at 200°C for 4 hours to produce carrier precursor C. 50 mL of an aqueous solution containing 2.71 g of zirconium chloride was added to 100 g of carrier precursor C, dried at 90°C for 8 h, and then calcined at 800°C for 3 h under a nitrogen atmosphere to obtain a spherical carrier with a particle size of 0.6-0.7 mm. The carrier yield and attrition data are shown in Table 1.

[0069] (2) Catalyst preparation

[0070] Dissolve 2.43 g of phosphoric acid H3PO4 (concentration 85 wt%) in 50 mL of water, then add 6.59 g of molybdenum trioxide and 2.91 g of basic nickel carbonate, heat to 100 ° C and stir under reflux for 2.0 h, filter and adjust the volume to 85 mL to obtain a Mo-Ni-P aqueous solution.

[0071] The Mo-Ni-P aqueous solution was added to 100 g of the prepared support, mixed thoroughly, and allowed to stand for 3 hours. The mixture was then dried at 110°C for 4 hours and calcined at 550°C for 3 hours to obtain a catalyst with a MoO3 content of 6.0 wt%, a NiO content of 1.5 wt%, and a P content of 0.6 wt%. The catalyst's physical and chemical properties are shown in Table 2.

[0072] (3) Catalyst evaluation

[0073] The catalyst activity was evaluated over a long period using a pilot hydrogenation unit with a run time of 1500 h. The catalyst evaluation conditions were: reaction temperature 420°C, reaction pressure 15.0 MPa, and volume space velocity 0.3 h-1. -1 The hydrogen-to-oil volume ratio was 500:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0074] Example 3

[0075] (1) Vector preparation

[0076] Pseudo-boehmite powder (specific surface area 308m 2 / g, pore volume 1.02 mL / g) was rolled in a ball mill to produce spherical carrier precursor A with a diameter of 0.4-0.5 mm. 52.5 g of corn starch was mixed with 50 g of a 25 wt% aqueous solution of ammonium bicarbonate and then mixed with 300 g of pseudo-boehmite powder to produce a mixture. 3.5 g of corn starch was added to 100 g of water and heated at 70°C for 20 minutes to produce an aqueous solution of organic polymer B. 100 g of carrier precursor A was placed in a ball mill and evenly sprinkled with the mixture and the aqueous solution of organic polymer B during rolling. The ball mill was rotated at 30 rpm. After balling, carrier precursor B with a diameter of 0.6-0.7 mm was produced. Carrier precursor B was subjected to a low-temperature heat treatment at 200°C for 4 hours to produce carrier precursor C. 50 mL of an aqueous solution containing 4.08 g of zirconium sulfate was added to 100 g of carrier precursor C, dried at 90°C for 8 h, and then calcined at 850°C for 3 h under a nitrogen atmosphere to obtain a spherical carrier with a particle size of 0.6-0.7 mm. The carrier yield and attrition data are shown in Table 1.

[0077] (2) Catalyst preparation

[0078] Dissolve 4.30 g of phosphoric acid H3PO4 (concentration 85 wt%) in 50 mL of water, then add 11.68 g of molybdenum trioxide and 5.16 g of basic nickel carbonate, heat to 100 ° C and stir under reflux for 2.0 h, filter and adjust the volume to 85 mL to obtain a Mo-Ni-P aqueous solution.

[0079] The Mo-Ni-P aqueous solution was added to 100 g of the prepared support, mixed evenly, and allowed to stand for 3 h. The mixture was then dried at 110 °C for 4 h and calcined at 550 °C for 3 h to obtain a catalyst having a MoO3 content of 10.0 wt%, a NiO content of 2.5 wt%, and a P content of 1.0 wt%. The physicochemical properties of the catalyst are shown in Table 2, and the distribution of MoO3 on the catalyst is shown in Table 2. Figure 1 and Figure 2 .

[0080] (3) Catalyst evaluation

[0081] The catalyst activity was evaluated over a long period using a pilot hydrogenation unit with a run time of 1500 h. The catalyst evaluation conditions were: reaction temperature 420°C, reaction pressure 15.0 MPa, and volume space velocity 0.3 h-1. -1 The hydrogen-to-oil volume ratio was 500:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0082] Example 4

[0083] (1) Vector preparation

[0084] Pseudo-boehmite powder (specific surface area 308m 2 / g, pore volume 1.02mL / g) was rolled in a ball mill to produce spherical carrier precursor A with a diameter of 0.4-0.5mm. 175g of corn starch was mixed with 150g of a 25wt% aqueous solution of ammonium bicarbonate and then mixed with 1000g of pseudo-boehmite powder to obtain a mixture. 3.5g of corn starch was added to 100g of water and heated at 70°C for 20 minutes to obtain an aqueous solution of organic polymer B. 100g of carrier precursor A was placed in a ball mill and evenly sprinkled with the mixture and the aqueous solution of organic polymer B during rolling. The ball mill was rotated at 30 rpm. After balling, carrier precursor B with a diameter of 0.9-1.0mm was obtained. Carrier precursor B was subjected to a low-temperature heat treatment at 200°C for 4 hours to obtain carrier precursor C. 50 mL of an aqueous solution containing 4.93 g of zirconium nitrate was added to 100 g of carrier precursor C, dried at 90°C for 8 h, and then calcined at 850°C for 3 h under a nitrogen atmosphere to obtain a spherical carrier with a particle size of 0.9-1.0 mm. The carrier yield and attrition data are shown in Table 1.

[0085] (2) Catalyst preparation

[0086] Dissolve 4.30 g of phosphoric acid H3PO4 (concentration 85 wt%) in 50 mL of water, then add 11.68 g of molybdenum trioxide and 5.16 g of basic nickel carbonate, heat to 100 ° C and stir under reflux for 2.0 h, filter and adjust the volume to 85 mL to obtain a Mo-Ni-P aqueous solution.

[0087] The Mo-Ni-P aqueous solution was added to 100 g of the prepared support, mixed thoroughly, and allowed to stand for 3 hours. The mixture was then dried at 110°C for 4 hours and calcined at 550°C for 3 hours to obtain a catalyst with a MoO3 content of 10.0 wt%, a NiO content of 2.5 wt%, and a P content of 1.0 wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0088] (3) Catalyst evaluation

[0089] The catalyst activity was evaluated over a long period using a pilot hydrogenation unit with a run time of 1500 h. The catalyst evaluation conditions were: reaction temperature 420°C, reaction pressure 15.0 MPa, and volume space velocity 0.3 h-1. -1 The hydrogen-to-oil volume ratio was 500:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0090] Example 5

[0091] The reaction was essentially the same as Example 3, except that 52.5 g of corn starch was replaced with 52.5 g of potato starch, 3.5 g of corn starch was replaced with 3.5 g of potato starch, and 4.93 g of zirconium nitrate was replaced with 4.08 g of zirconium sulfate. A spherical carrier with a particle size of 0.6 to 0.7 mm was prepared. The carrier yield and attrition data are shown in Table 1. The resulting catalyst had a MoO3 content of 10.0 wt%, a NiO content of 2.5 wt%, and a P content of 1.0 wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0092] The catalyst evaluation was the same as in Example 3. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0093] Example 6

[0094] The reaction was essentially the same as in Example 3, except that 52.5 g of corn starch was replaced with 44.19 g of methyl cellulose, and 3.5 g of corn starch was replaced with 2.95 g of methyl cellulose. A spherical carrier with a particle size of 0.6 to 0.7 mm was prepared. The carrier yield and attrition data are shown in Table 1. The resulting catalyst had a MoO3 content of 10.0 wt%, a NiO content of 2.5 wt%, and a P content of 1.0 wt%. The catalyst's physicochemical properties are shown in Table 2.

[0095] The catalyst evaluation was the same as in Example 3. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0096] Comparative Example 1

[0097] (1) Vector preparation

[0098] Pseudo-boehmite powder (specific surface area 308m 2 / g, pore volume 1.02 mL / g) was rolled in a ball mill to produce spherical carrier precursor A with a diameter of 0.4-0.5 mm. 31.5 g of corn starch was mixed with 15 g of 5 wt% ammonia water and then with 300 g of pseudo-boehmite powder to obtain a mixture. 100 g of carrier precursor A was placed in a ball mill and evenly sprinkled with the mixture, 3.5 g of corn starch, and water while rolling at 30 rpm. After balling, carrier precursor B with a diameter of 0.6-0.7 mm was obtained. Carrier precursor B was subjected to low-temperature heat treatment at 200°C for 4 hours to obtain carrier precursor C. 50 mL of an aqueous solution containing 4.93 g of zirconium nitrate was added to 100 g of carrier precursor C, dried at 90°C for 8 h, and then calcined at 750°C for 3 h under a nitrogen atmosphere to obtain a spherical carrier with a particle size of 0.6-0.7 mm. The carrier yield and attrition data are shown in Table 1.

[0099] (2) Catalyst preparation

[0100] Dissolve 1.57 g of phosphoric acid H3PO4 (concentration 85 wt%) in 50 mL of water, then add 4.27 g of molybdenum trioxide and 1.88 g of basic nickel carbonate, heat to 100 ° C and stir under reflux for 2.0 h, filter and adjust the volume to 85 mL to obtain a Mo-Ni-P aqueous solution.

[0101] The Mo-Ni-P aqueous solution was added to 100 g of the prepared support, mixed thoroughly, and allowed to stand for 3 hours. The mixture was then dried at 110°C for 4 hours and calcined at 550°C for 3 hours to obtain a catalyst with a MoO3 content of 4.0 wt%, a NiO content of 1.0 wt%, and a P content of 0.4 wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0102] (3) Catalyst evaluation

[0103] The catalyst activity was evaluated over a long period using a pilot hydrogenation unit with a run time of 1500 h. The catalyst evaluation conditions were: reaction temperature 420°C, reaction pressure 15.0 MPa, and volume space velocity 0.3 h-1. -1 The hydrogen-to-oil volume ratio was 500:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0104] Comparative Example 2

[0105] (1) Vector preparation

[0106] Pseudo-boehmite powder (specific surface area 308m 2 / g, pore volume 1.02mL / g) was rolled in a ball mill to produce spherical carrier precursor A with a diameter of 0.4-0.5mm. 31.5g of corn starch was mixed with 300g of pseudo-boehmite powder to obtain a mixture. 3.5g of corn starch was added to 100g of water and heated at 70°C for 20min to obtain an aqueous solution of organic polymer B. 100g of carrier precursor A was placed in a ball mill and the mixture and the aqueous solution of organic polymer B were evenly sprinkled into the mixture while rolling at a speed of 30 rpm. After balling, carrier precursor B with a diameter of 0.6-0.7mm was obtained. Carrier precursor B was dried at 120°C for 4h to obtain carrier precursor C. 50 mL of an aqueous solution containing 4.93 g of zirconium nitrate was added to 100 g of carrier precursor C, dried at 90°C for 8 h, and then calcined at 750°C for 3 h under a nitrogen atmosphere to obtain a spherical carrier with a particle size of 0.6-0.7 mm. The carrier yield and attrition data are shown in Table 1.

[0107] (2) Catalyst preparation

[0108] Dissolve 1.57 g of phosphoric acid H3PO4 (concentration 85 wt%) in 50 mL of water, then add 4.27 g of molybdenum trioxide and 1.88 g of basic nickel carbonate, heat to 100 ° C and stir under reflux for 2.0 h, filter and adjust the volume to 85 mL to obtain a Mo-Ni-P aqueous solution.

[0109] The Mo-Ni-P aqueous solution was added to 100 g of the prepared support, mixed thoroughly, and allowed to stand for 3 hours. The mixture was then dried at 110°C for 4 hours and calcined at 550°C for 3 hours to obtain a catalyst with a MoO3 content of 4.0 wt%, a NiO content of 1.0 wt%, and a P content of 0.4 wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0110] (3) Catalyst evaluation

[0111] The catalyst activity was evaluated over a long period using a pilot hydrogenation unit with a run time of 1500 h. The catalyst evaluation conditions were: reaction temperature 420°C, reaction pressure 15.0 MPa, and volume space velocity 0.3 h-1. -1 The hydrogen-to-oil volume ratio was 500:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0112] Table 1 Carrier yield and attrition

[0113]

[0114] Table 2 Physicochemical properties of catalysts

[0115]

[0116] Table 3 Properties of crude oil

[0117]

[0118] Table 4 Catalyst evaluation results

[0119]

[0120] The activity of Comparative Example 1 was set as 100, and the evaluation results of the other comparative examples were compared with each other are shown in Table 4.

Claims

1. A method for preparing an ebullated bed heavy oil hydrogenation catalyst, comprising the following steps: (1) Pseudo-boehmite powder is spherical-molded to obtain a carrier precursor A; (2) Mixing an organic high molecular polymer A, a nitrogen-containing weak base compound, and pseudo-boehmite powder to obtain a mixed material; the nitrogen-containing weak base compound is one or a mixture of two or more of ammonia water, ammonium carbonate, and ammonium bicarbonate; (3) placing the carrier precursor A obtained in step (1) into a ball rolling machine, and uniformly adding the mixed material obtained in step (2) and the aqueous solution of the heat-treated organic polymer B during the rolling process to obtain the carrier precursor B; the aqueous solution of the heat-treated organic polymer B is prepared by adding the organic polymer B to water, heating and mixing at 60 to 100° C. for 10 to 40 minutes, and obtaining the aqueous solution of the heat-treated organic polymer B after the organic polymer B is completely dissolved; (4) subjecting the carrier precursor B obtained in step (3) to low-temperature heat treatment to obtain a carrier precursor C; (5) mixing the carrier precursor C obtained in step (4) with a soluble zirconium salt solution, drying the mixture, and calcining the mixture under an inert atmosphere to obtain a carrier; (6) introducing an active metal component onto the support obtained in step (5), followed by drying and calcining to obtain a hydrogenation catalyst, wherein an additive P is introduced when introducing the active metal component, and the active metal component is one or more of Group VIB metals and / or Group VIII metals; in, The organic high molecular polymer A is one or more of starch, sugar, cellulose ether and flour; the organic high molecular polymer B is one or more of starch, sugar, cellulose ether and flour.

2. The method for preparing the ebullated bed heavy oil hydrogenation catalyst according to claim 1, wherein: The pseudo-boehmite powders in step (1) and step (2) are pseudo-boehmite powders of the same nature, or pseudo-boehmite powders of different natures.

3. The method for preparing the ebullated bed heavy oil hydrogenation catalyst according to claim 1, wherein: The spherical forming in step (1) is carried out by one or more of the following methods: extrusion spherical forming, rolling forming, and spray drying forming.

4. The method for preparing the ebullated bed heavy oil hydrogenation catalyst according to claim 1, wherein: The particle size of the carrier precursor A in step (1) is 0.1 to 1.0 mm.

5. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1 or 4, characterized in that: The particle size of the carrier precursor A in step (1) is 0.3 to 0.7 mm.

6. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: The organic high molecular polymer A is starch.

7. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1 or 6, characterized in that: The starch is one or more of mung bean starch, tapioca starch, sweet potato starch, potato starch, wheat starch, water chestnut starch, lotus root starch and corn starch.

8. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1 or 6, characterized in that: The starch is corn starch and / or potato starch.

9. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: The cellulose ether is at least one of methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose and phenyl cellulose, and the sugar is one or more of monosaccharides, disaccharides and polysaccharides.

10. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1 or 9, characterized in that: The cellulose ether is methyl cellulose and the sugar is glucose.

11. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: The nitrogen-containing weak base compound in step (2) is ammonia water.

12. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, characterized in that: The concentration of the nitrogen-containing weak base compound aqueous solution in step (2) is 2 wt% to 40 wt%.

13. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, characterized in that: The concentration of the nitrogen-containing weak base compound aqueous solution in step (2) is 5 wt % to 30 wt %.

14. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: The mass ratio of the organic high molecular polymer A to the nitrogen-containing weak base compound in step (2) is 1:0.05 to 1:0.

5.

15. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, characterized in that: The amount of the organic high molecular polymer A and the nitrogen-containing weak base compound added in step (2) is 5 wt% to 40 wt% of the dry mass of the pseudo-boehmite powder.

16. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, characterized in that: The amount of the organic high molecular polymer A and the nitrogen-containing weak base compound added in step (2) is 10 wt% to 30 wt% of the dry mass of the pseudo-boehmite powder.

17. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, characterized in that: The concentration of the aqueous solution of the organic high molecular polymer B after the heat treatment in step (3) is 0.5 wt % to 8 wt %.

18. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1 or 17, characterized in that: The concentration of the aqueous solution of the organic high molecular polymer B after the heat treatment in step (3) is 1 wt% to 5 wt%.

19. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, characterized in that: The mass ratio of the added amount of the aqueous solution of the organic high molecular polymer B after the heat treatment to the mixed material in step (3) is 0.5 to 1.

5.

20. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, characterized in that: The low-temperature heat treatment temperature in step (4) is 100-300°C, and the treatment time is 3-12 hours.

21. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, characterized in that: The low-temperature heat treatment temperature in step (4) is 150-250° C., and the treatment time is 3-12 hours.

22. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, characterized in that: The soluble zirconium salt in step (5) is one or more of zirconium nitrate, zirconium chloride and zirconium sulfate.

23. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, characterized in that: The drying temperature in step (5) is 60-120° C.; the calcination in step (5) is carried out under an inert atmosphere, which is one or more of nitrogen, helium, neon, argon, krypton, and xenon; the calcination temperature is 600-900° C.; and the calcination time is 1-5 hours.

24. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, characterized in that: The particle size of the carrier in step (5) is 0.2 to 2.0 mm.

25. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1 or 24, characterized in that: The particle size of the carrier in step (5) is 0.3 to 1.8 mm.

26. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, characterized in that: The Group VIB metal is Mo and / or W, and the Group VIII metal is Ni and / or Co.

27. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, characterized in that: The active metal components in step (6) are Mo and Ni.

28. The method for preparing an ebullated-bed heavy oil hydrogenation catalyst according to claim 1, characterized in that: The drying in step (6) is carried out at 80-120° C. for 4-12 hours; the roasting temperature in step (6) is 400-600° C., the roasting time is 1-5 hours, and the roasting is carried out in the presence of an oxygen-containing atmosphere.

29. An ebullated-bed heavy oil hydrogenation catalyst obtained by the preparation method according to any one of claims 1 to 28.

30. The ebullated-bed heavy oil hydrogenation catalyst according to claim 29, characterized in that: The properties of the ebullient bed heavy oil hydrogenation catalyst are as follows: the specific surface area is 140 to 250 m 2 / g, the pore volume is 0.60-0.90mL / g, and the pore volume of pores with a pore diameter greater than 50nm accounts for more than 3% of the total pore volume.

31. Use of the ebullated-bed heavy oil hydrogenation catalyst according to any one of claims 29 to 30 in a heavy oil hydrogenation process.

32. The use according to claim 31, characterized in that: The heavy oil is one or more of atmospheric residue oil, vacuum residue oil, catalytic slurry oil and coal tar.

33. The use according to claim 31, characterized in that: The process conditions of the hydrotreatment process are as follows: reaction pressure is 10-20 MPa, temperature is 300-500℃, liquid hourly volume space velocity is 0.1-1.5h -1 , the hydrogen-to-oil volume ratio is 300-1000.

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