Hydrocracking catalyst, process for its preparation and crude oil hydrocracking process

Abstract

This invention discloses a hydrocracking catalyst and its preparation method, as well as a crude oil hydrocracking process. The preparation method includes the following steps: (1) preparing spherical material A; (2) preparing a first modified organic polymer and a second modified organic polymer; (3) placing material A in a ball rolling machine, and uniformly introducing the first modified organic polymer, the second modified organic polymer, boehmite powder, and a heated organic polymer aqueous solution while rolling, and obtaining material B after treatment; (5) subjecting material B to low-temperature heat treatment, then mixing it with an iron-containing compound, drying and calcining to obtain a support, further introducing a hydrogenation metal component, and then drying and calcining to obtain a hydrocracking catalyst. A hydrocracking catalyst is also provided, comprising a hydrogenation metal component, an auxiliary agent iron oxide, a support, and optionally phosphorus pentoxide. The hydrocracking catalyst provided by this invention has a spherical core-shell structure, possessing high cracking activity, strong impurity removal capacity, and containment capacity, making it suitable for direct hydrocracking reactions using crude oil as feedstock.

Description

Technical Field

[0001] This invention belongs to the field of oil refining technology and relates to a hydrocracking catalyst and its preparation method, particularly to a hydrocracking catalyst for processing crude oil in a hydrocracking process and its preparation method. Background Technology

[0002] Crude oil is a viscous, oily liquid, dark brown with a greenish fluorescence and a distinctive odor. It is a mixture of various liquid hydrocarbons, including alkanes, cycloalkanes, aromatics, and alkenes. Its main components are carbon and hydrogen, accounting for 83-87% and 11-14% respectively; it also contains trace amounts of sulfur, oxygen, nitrogen, and elements such as phosphorus, arsenic, potassium, sodium, calcium, magnesium, nickel, iron, and vanadium. After refining, crude oil can be processed into various fuel oils, solvent oils, lubricating oils, greases, paraffin wax, asphalt, liquefied petroleum gas (LPG), and aromatics, providing fuel, raw materials, and chemical products for various sectors of the national economy. Crude oil can be classified into three categories based on composition: paraffin-based crude oil, naphthenic crude oil, and intermediate-based crude oil; four categories based on sulfur content: ultra-low sulfur crude oil, low sulfur crude oil, sulfur-containing crude oil, and high sulfur crude oil; and three categories based on specific gravity: light crude oil, medium crude oil, and heavy crude oil.

[0003] Currently, most of the world's conventional crude oil is under development and at a relatively high level of extraction. However, with the development of the global economy, energy consumption has increased significantly, and the huge energy gap will mainly be filled by heavy crude oil. The imported crude oil processed domestically is gradually becoming heavier and of lower quality, making the effective processing of heavy crude oil a major concern for refineries.

[0004] In recent years, the demand for gasoline and diesel fuels in my country has slowed down year by year, and the market demand for vehicle fuel oil is expected to decrease further. Meanwhile, the development of the national economy has led to consumption upgrades, resulting in a sustained increase in demand for olefins and aromatics, which can be used as monomers for various synthetic materials. This necessitates the transformation of refineries from fuel oil-based to fuel oil-chemical and all-chemical refineries, with a gradual increase in the proportion of chemical products in the refinery's product structure. Faced with the urgent need for refinery transformation, the currently widely used fixed-bed hydrotreating units can no longer meet the requirements of enterprises, facing the risks of high investment costs for unit upgrades or the inability to produce qualified chemical feedstocks after upgrades. In contrast, fluidized bed hydrotreating technology has advantages such as strong adaptability to feedstocks, good mass and heat transfer, online catalyst addition and removal, high catalyst utilization, long operating cycles, and flexible unit operation. It is suitable for the hydrotreating of heavy crude oil, achieving the goal of lightening heavy oil and producing more chemical feedstocks.

[0005] In crude oil hydrocracking technology, the catalyst is the core technology. Currently, most hydrocracking catalysts use molecular sieves or amorphous silica-alumina as the core, but these catalysts have poor tolerance to impurities. Crude oil contains oxygen-containing substances such as naphthenic acids and phenols, and the water produced after hydrogenation can cause the molecular sieve framework to collapse. Moreover, basic nitrogen and metal heteroatoms in crude oil can poison the active centers of molecular sieve catalysts, and a single catalyst cannot meet the requirements; therefore, catalyst gradation is necessary to solve the problem.

[0006] CN202210024883.4 discloses a crude oil hydrocracking catalyst and its preparation method. The catalyst comprises a support and an active metal component, wherein the support is a silicon-aluminum material, and the active component is at least one metal selected from Group VIB and Group VIII of the periodic table. The preparation method involves first preparing the silicon-aluminum material, then mixing the obtained silicon-aluminum material, binder, and active metal component, followed by drying and calcination to obtain the crude oil hydrocracking catalyst. The catalyst has advantages such as strong impurity tolerance, high removal rate, and good cracking performance, while also featuring a simple production process and low energy consumption.

[0007] CN200810246528.1 discloses a method for hydrocracking heavy crude oil, aiming to solve the problems of difficulty in processing heavy crude oil with an API gravity of less than 20 and rapid catalyst deactivation in a fixed bed. The heavy crude oil, in the presence of hydrogen, sequentially passes through a hydroprotectant, a hydrodemetallizing agent, a hydrodesulfurizing agent I, a hydrocracking agent, and a hydrodesulfurizing agent II. This patent uses a fixed bed and catalyst gradation scheme to process heavy crude oil, which suffers from bed pressure drop and hot spots affecting long-term operation, and has high viscosity requirements for the crude oil, resulting in poor adaptability. Summary of the Invention

[0008] To overcome the shortcomings of existing technologies, the main objective of this invention is to provide a hydrocracking catalyst, its preparation method, and a crude oil hydrocracking process. The hydrocracking catalyst provided by this invention has a spherical core-shell structure, with an amorphous silica-alumina core and an alumina shell containing both mesopores and macropores. This hydrocracking catalyst possesses high cracking activity, strong impurity removal capacity, and high containment capacity. Furthermore, its abundant hierarchical pore structure can accommodate hydrogenation reactions of different fractions, making it particularly suitable for direct hydrocracking reactions using crude oil as feedstock.

[0009] The first aspect of this invention provides a method for preparing a hydrocracking catalyst, the method comprising the following steps:

[0010] (1) Under contact conditions, the organic polymer aqueous solution after heat treatment is mixed with amorphous silicon aluminum, and then spherical material A is obtained after molding treatment;

[0011] (2) The organic polymer is added to an acidic solution for a first modification treatment, and the first modified organic polymer is obtained after the treatment;

[0012] (3) The organic polymer is added to an aqueous solution of a nitrogen-containing weakly alkaline compound for a second modification treatment, and the second modified organic polymer is obtained after the treatment.

[0013] (4) Under the rolling ball forming condition, material A is placed in the ball rolling machine, and while rolling, the first modified organic polymer obtained in step (2), the second modified organic polymer obtained in step (3), pseudoboehmite powder and the organic polymer aqueous solution after heat treatment are uniformly introduced, and material B is obtained after treatment.

[0014] (5) Material B is subjected to low-temperature heat treatment to obtain material C;

[0015] (6) Mix material C with an iron-containing compound, and after uniform mixing, dry and calcine to obtain a carrier;

[0016] (7) After introducing hydrogenated metal components onto the support obtained in step (6), the catalyst is dried and calcined to obtain a hydrocracking catalyst.

[0017] Preferably, according to a specific embodiment of the present invention, the amorphous silicon-aluminum used in step (1) can be a commercially available commodity, or it can be amorphous silicon-aluminum prepared according to methods disclosed in existing literature. In the present invention, the preferred properties of the amorphous silicon-aluminum are as follows: specific surface area of ​​250-320 m² / g. 2 / g, pore volume is 0.7~1.0mL / g, and silicon oxide content is 10wt%~50wt%; usually, before use, it is preferred to control the particle size of amorphous silica-alumina to be above 200 mesh.

[0018] Preferably, according to a specific embodiment of the present invention, the organic polymer is one or more of starch, cellulose ether, and flour, preferably starch. Further, the starch may be derived from 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, preferably corn starch and / or potato starch; the cellulose ether may be derived from at least one of methylcellulose, hydroxyethyl methylcellulose, carboxymethyl cellulose, ethylcellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenylcellulose, preferably methylcellulose.

[0019] Preferably, according to a specific embodiment of the present invention, the mass concentration of the organic polymer aqueous solution after heat treatment in steps (1) and (4) is 0.5% to 8.0%, preferably 1.0% to 5.0%.

[0020] Preferably, according to a specific embodiment of the present invention, the specific preparation process of the organic polymer aqueous solution after heat treatment in steps (1) and (4) is as follows: under heat treatment conditions, the organic polymer is mixed with water until the organic polymer dissolves, and then the organic polymer aqueous solution after heat treatment is obtained, wherein the heat treatment temperature is 60-100°C and the heat treatment time is 10-40 minutes.

[0021] Preferably, according to a specific embodiment of the present invention, the mass ratio of the organic polymer aqueous solution to the amorphous silica-alumina in step (1) is 0.5 to 1.5.

[0022] Preferably, according to a specific embodiment of the present invention, the molding in step (1) can be performed by at least one of extrusion ball-throwing molding and roll forming; there are no special restrictions on the molding, and those skilled in the art can adjust the molding process conditions according to actual needs.

[0023] Preferably, according to a specific embodiment of the present invention, in step (2), the organic polymer is added to an acidic solution for a first modification treatment. After the treatment is completed, the polymer is cooled, optionally washed with water, and dried to obtain the first modified organic polymer. Further, the acidic solution can be an inorganic acid and / or an organic acid, wherein the inorganic acid can be selected from one or a mixture of two or more of hydrochloric acid, sulfuric acid, and nitric acid, preferably hydrochloric acid; the organic acid can be selected from one or a mixture of two or more of citric acid, acetic acid, malic acid, lactic acid, and tartaric acid, preferably citric acid.

[0024] Preferably, according to a specific embodiment of the present invention, the temperature of the first modification treatment in step (2) is 30 to 50°C; and the time of the first modification treatment is 2 to 6 hours.

[0025] Preferably, according to a specific embodiment of the present invention, the concentration of the acidic solution in step (2) is 5wt% to 40wt%; the mass ratio of the organic polymer to the acidic solution is 1:0.1 to 1:5.

[0026] Preferably, according to a specific embodiment of the present invention, the nitrogen-containing weakly basic compound in step (3) can be selected from at least one of ammonia, ammonium carbonate, and ammonium bicarbonate, preferably ammonia. The mass ratio of the organic polymer to the nitrogen-containing weakly basic compound is 1:0.05 to 1:0.5. The concentration of the aqueous solution of the nitrogen-containing weakly basic compound is 2wt% to 40wt%, preferably 5wt% to 35wt%.

[0027] Preferably, according to a specific embodiment of the present invention, the pseudoboehmite powder in step (4) can be a commercially available product, or it can be prepared according to the methods described in existing published patents and documents. Preferably, in the present invention, the properties of the pseudoboehmite powder after calcination at 550-750°C are as follows: specific surface area of ​​260-320 m². 2 / g, with a pore volume of 0.7~1.0mL / g.

[0028] Preferably, according to a specific embodiment of the present invention, the amount of the first modified organic polymer added in step (4) (by mass) is 10wt% to 20wt% of the dry basis mass of the pseudoboehmite powder.

[0029] Preferably, according to a specific embodiment of the present invention, the amount of the second modified organic polymer added in step (4) (by mass) is 5wt% to 15wt% of the dry basis mass of the pseudoboehmite powder.

[0030] Preferably, according to a specific embodiment of the present invention, the ratio of the amount of the heated organic polymer aqueous solution added in step (4) to the mass of the pseudoboehmite powder is 0.8 to 1.5.

[0031] Preferably, according to a specific embodiment of the present invention, the low-temperature heat treatment temperature in step (5) is 100-300°C, preferably 150-250°C; the treatment time is 3-12 hours.

[0032] Preferably, according to a specific embodiment of the present invention, the iron-containing compound in step (6) is a soluble iron salt, and more specifically, the iron-containing compound may be selected from one or more of ferric nitrate, ferric chloride, ferric acetate, ferric sulfate, etc.

[0033] Preferably, according to a specific embodiment of the present invention, the drying temperature in step (6) is 70 to 120°C.

[0034] Preferably, according to a specific embodiment of the present invention, the calcination in step (6) is carried out in the presence of an inert atmosphere, which is one or more of nitrogen, helium, neon, argon, krypton, and xenon, preferably nitrogen. The calcination temperature is 600-800°C, and the calcination time is 1-5 hours.

[0035] Preferably, according to a specific embodiment of the present invention, the specific method of introducing the hydrogenated metal component onto the carrier obtained in step (6) in step (7) is not particularly limited, and can be any method conventionally used in the art. Those skilled in the art can choose according to actual needs, such as impregnation. The present invention does not particularly limit the specific implementation of the impregnation method, and can employ any method conventionally used in the art, for example, co-impregnation or stepwise impregnation can be used to introduce the hydrogenated metal component. The impregnation can be saturated impregnation or supersaturated impregnation.

[0036] Preferably, according to a specific embodiment of the present invention, in step (7), the carrier is impregnated with an impregnation solution containing a precursor of hydrogenated metal components, and the resulting solid product is dried and calcined.

[0037] Preferably, according to a specific embodiment of the present invention, the selection of the precursor of the hydrogenated metal component is not particularly limited, and it can be a soluble metal salt of the hydrogenated metal component. The impregnation conditions are not particularly limited, and those skilled in the art can make appropriate selections according to specific circumstances.

[0038] Preferably, according to a specific embodiment of the present invention, the impregnation solution contains a phosphorus-containing compound. There is no particular limitation on the type of phosphorus-containing compound; phosphoric acid is used as an example in this invention for illustrative purposes, but the invention is not limited thereto.

[0039] Preferably, according to a specific embodiment of the present invention, the range of selection for the hydrogenation metal component is wide, and it can be various active metal components commonly used in the field of hydrogenation. Those skilled in the art can make appropriate selections according to specific application conditions. Preferably, the active metal component includes at least one of Group VIII metals and at least one of Group VIB metals. More preferably, the Group VIII metal is Ni and / or Co, and the Group VIB metal is W and / or Mo.

[0040] Preferably, according to a specific embodiment of the present invention, the precursor of the hydrogenated 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, and 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 is basic nickel carbonate and / or nickel nitrate; and the cobalt-containing compound is basic cobalt carbonate and / or cobalt nitrate. The phosphorus-containing compound can be one or more of phosphoric acid, ammonium dihydrogen phosphate, and ammonium monohydrogen phosphate. The concentration of the hydrogenated metal component in the aqueous solution containing the hydrogenated metal component and P is 0.05–1.0 g / mL (calculated as hydrogenated metal oxide), and the concentration of P is 0–0.1 g / mL, preferably 0.002–0.1 g / mL.

[0041] Preferably, according to a specific embodiment of the present invention, the drying in step (7) is to dry the material at a temperature of 80 to 140°C for 4 to 12 hours.

[0042] Preferably, according to a specific embodiment of the present invention, the roasting in step (7) is a roasting treatment of the material at a temperature of 400-600°C for 1-5 hours. The roasting is carried out in the presence of an oxygen-containing atmosphere, such as in air.

[0043] A second aspect of the present invention provides a hydrocracking catalyst obtained by the above preparation method.

[0044] Preferably, according to a specific embodiment of the present invention, the hydrocracking catalyst includes a hydrogenation metal component, an auxiliary iron oxide, a support, and optionally phosphorus pentoxide. The hydrogenation metal component is at least one of Group VIB metals and at least one of Group VIII metals. The support is an amorphous silica-alumina and alumina composite support, wherein the hydrogenation metal component exists on the support in the form of an oxide.

[0045] Preferably, according to a specific embodiment of the present invention, the composite support for the hydrocracking catalyst has a spherical core-shell structure, wherein the core layer is amorphous silica-alumina, and the shell layer is alumina with a two-level pore distribution of mesopores and macropores. Based on the weight of the support, the content of amorphous silica-alumina in the core layer is 30% to 70%; and the content of alumina in the shell layer is 30% to 70%.

[0046] Preferably, according to a specific embodiment of the present invention, based on the weight of the catalyst and calculated as oxides, the content of the Group VIB metal component is 10wt% to 25wt%; the content of the Group VIII metal component is 2wt% to 7wt%; and the content of phosphorus pentoxide is 2.0wt% to 6.0wt%. The content of the auxiliary agent iron oxide is 0.1wt% to 3.0wt% of the carrier.

[0047] Preferably, according to a specific embodiment of the present invention, the Group VIB metal is generally Mo and / or W, and the Group VIII metal is generally Ni and / or Co.

[0048] Preferably, according to a specific embodiment of the present invention, the hydrocracking catalyst has the following properties: a specific surface area of ​​150–220 m². 2 / g, with a pore volume of 0.40–0.90 mL / g. Mesopores with a pore size of 10–50 nm account for 60%–90% of the total pore volume, while macropores with a pore size greater than 50 nm account for 5%–10% of the total pore volume.

[0049] Preferably, according to a specific embodiment of the present invention, the active metal distribution of the hydrocracking catalyst is relatively less on the outside and relatively more on the inside, exhibiting an uneven distribution.

[0050] A third aspect of the present invention provides an application of the above-mentioned hydrocracking catalyst in the hydrocracking process of hydrocarbon oil, wherein hydrocarbon oil and hydrogen are reacted in the presence of the above-mentioned hydrocracking catalyst or the hydrocracking catalyst obtained according to the above preparation method under hydrocracking reaction conditions.

[0051] The fourth aspect of the present invention provides a crude oil fluidized bed hydrogenation process, wherein crude oil and hydrogen are mixed and then fed into a fluidized bed reactor for hydrogenation reaction, wherein the fluidized bed reactor is filled with the above-mentioned hydrocracking catalyst or the hydrocracking catalyst prepared according to the above-mentioned preparation method.

[0052] Preferably, according to a specific embodiment of the present invention, the crude oil may be selected from one or more of high-acid crude oil, high-calcium crude oil, and high-sulfur crude oil.

[0053] Preferably, according to a specific embodiment of the present invention, the hydrogenation reaction conditions are: a reaction pressure of 10–20 MPa, a reaction temperature of 360–430 °C, and a liquid hourly space velocity of 0.1–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300–800.

[0054] The technical advantages and effects of the hydrocracking catalyst and its preparation method provided by this invention are reflected in the following aspects:

[0055] 1. In the preparation method of the hydrocracking catalyst provided by the present invention, the organic polymer is decomposed into small molecules in water after being heated, so that its aqueous solution exhibits high adhesion, which can enhance the interaction between amorphous silicon and aluminum materials, and at the same time strengthen the interaction force between pseudoboehmite powder and amorphous silicon and aluminum, thereby improving the overall strength and wear resistance of the composite carrier.

[0056] 2. In the preparation method of the hydrocracking catalyst provided by the present invention, the organic polymer molecules after acid modification become smaller and the adhesion weakens. When mixed with boehmite powder, it can increase the proportion of mesopores in the support during the subsequent preparation process. However, after the organic polymer reacts with the nitrogen-containing weakly basic compound, the molecular size does not change significantly, only the adhesion deteriorates. When mixed with boehmite powder, it only plays a pore-expanding role in the subsequent catalyst preparation process, which can increase the proportion of macropores in the support.

[0057] 3. In the preparation method of the hydrocracking catalyst provided by this invention, material B undergoes low-temperature treatment. The ammonia in the nitrogen-containing weakly basic compound that reacts with the organic polymer volatilizes and adsorbs onto the strongly acidic sites on alumina. With the addition of soluble iron salts, these iron salts interact with the ammonia on the alumina and adsorb onto the strongly acidic sites. After calcination, these iron salts occupy the strongly acidic sites on the alumina, weakening the interaction between the active metal and the alumina support and improving the utilization rate of the active metal. Simultaneously, the addition of iron increases the acidity of the alumina support, enhancing its cracking activity.

[0058] 4. In the preparation method of the hydrocracking catalyst provided by this invention, after calcination of the acid-modified organic polymer and the alkali-modified organic polymer under inert and oxygen-containing atmospheres, mesopores and macropores are generated in the alumina, which can expand the pores of the outer alumina and increase the proportion of mesopores and macropores in the alumina. Since the water absorption rate of carbon material is lower than that of alumina, the presence of carbon material in the support reduces the water absorption rate of the outer alumina support. During the impregnation process of active metal, the active metal adsorption on the outer alumina of the support is relatively small, while the adsorption on the inner amorphous silica-alumina of the support is relatively large. The active metal of the obtained catalyst is unevenly distributed, with relatively more active metal distributed inside the catalyst and relatively less active metal distributed on the outside of the catalyst. The hydrocracking activity of the catalyst exhibits a gradient distribution. The outer layer of the catalyst can effectively remove impurities such as metals, sulfur, and nitrogen from crude oil and perform mild hydrocracking, while protecting the inner layer of the catalyst. The inner layer of the catalyst can further hydrocrackle each fraction of crude oil, thereby achieving the removal of impurities and the stepwise hydrocracking reaction of crude oil.

[0059] 5. In the hydrocracking catalyst provided by the present invention, the inner layer of the support is amorphous silica-alumina, which has large pore volume, high specific surface area and high acid content; the outer layer of the support is alumina with a high proportion of mesopores and macropores and a certain acid content, which can effectively protect the inner catalyst. The catalyst has a non-uniform pore distribution and active metal distribution. When used for crude oil hydrocracking, it can remove impurities from crude oil and carry out stepwise hydrocracking reaction. Attached Figure Description

[0060] Figure 1 This is an electron probe microanalysis image of the catalyst cross-section in Example 3 of the present invention.

[0061] Figure 2 This is an electron probe scanning diagram of the catalyst cross-section MoO3 distribution in Example 3 of the present invention. Detailed Implementation

[0062] The technical solution and effects of the present invention are further illustrated below through specific embodiments. In the present invention, wt% is the mass fraction.

[0063] In this invention, the specific surface area and pore volume were measured using a cryogenic liquid nitrogen physical adsorption method, specifically a low-temperature nitrogen adsorption instrument (ASAP2420 model) from Micron Technology, USA. The specific procedure involved: a small sample was vacuum-treated at 300°C for 3-4 hours, and finally, the product was placed under liquid nitrogen cryogenic (-200°C) conditions for nitrogen adsorption-desorption testing. The surface area was obtained according to the BET equation, and the pore size distribution was obtained according to the BJH model.

[0064] The wear index of microsphere carriers smaller than 0.8 mm was tested using the high-speed air jet method (see ASTM D5757-00), while the wear index of microsphere carriers larger than 0.8 mm was measured using the drum method with a KM-ZV wear meter.

[0065] The distribution of active metals in the catalyst was detected using a JXA-8230 electron probe microanalyzer from NEC Corporation.

[0066] Example 1

[0067] (1) Carrier preparation

[0068] Weigh 80g of corn starch and add it to 2000g of water. Heat at 70℃ for 20 minutes to obtain a heat-treated aqueous solution of organic polymer. Add 400g of amorphous aluminum silica (specific surface area 290m²) to the solution. 2360g of a heated organic polymer aqueous solution (with a pore volume of 0.85mL / g) was mixed with 42g corn starch, 42g citric acid, and 140g water. After mixing, the mixture was heated to 40℃ for 3 hours, then filtered and washed with water, and dried at 40℃ for 24 hours to obtain the first modified organic polymer. 21.0g corn starch was mixed with 20g of 10wt% ammonia water to obtain the second modified organic polymer. Material A was placed in a ball rolling machine, and while rolling, the first modified organic polymer, the second modified organic polymer, and 600g of pseudoboehmite powder (specific surface area 310m²) were added evenly. 2 540g of an organic polymer aqueous solution (with a pore volume of 0.9mL / g) and heat-treated organic polymer were combined and spheroidized to obtain material B. Material B was then subjected to low-temperature heat treatment at 200℃ for 4h to obtain material C. 360mL of an aqueous solution containing 42.42g of ferric nitrate was added to material C, and the mixture was dried at 90℃ for 8h, followed by calcination at 650℃ for 3h under a nitrogen atmosphere to obtain spherical carriers with a particle size of 0.5~0.8mm. The carrier yield and wear data are shown in Table 1.

[0069] (2) Catalyst preparation

[0070] Dissolve 6.99 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 19.00 g of molybdenum trioxide and 8.39 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and make up to 85 mL to obtain Mo-Ni-P aqueous solution.

[0071] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 550℃ for 3h to obtain the catalyst, in which the content of MoO3 was 15.0wt%, the content of NiO was 3.75wt%, and the content of P was 1.5wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0072] (3) Catalyst evaluation

[0073] The catalyst was evaluated over a long period using a CSTR hydrogenation evaluation system, with an operating time of 1200 hours. The evaluation conditions were: reaction temperature 400℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.4 h⁻¹. -1 The hydrogen-to-oil volume ratio was 600:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0074] Example 2

[0075] (1) Carrier preparation

[0076] Weigh 80g of corn starch and add it to 2000g of water. Heat at 70℃ for 20 minutes to obtain a heat-treated aqueous solution of organic polymer. Add 500g of amorphous aluminum silicate (specific surface area 290 μm). 2 450g of a heated organic polymer aqueous solution (with a pore volume of 0.85mL / g) was mixed with 52.5g corn starch, 52.5g citric acid, and 175g water. After mixing, the mixture was heated to 40℃ for 3 hours, then filtered and washed with water, and dried at 40℃ for 24 hours to obtain the first modified organic polymer. 35.0g corn starch was mixed with 35g ammonia water with a concentration of 10wt% to obtain the second modified organic polymer. Material A was placed in a ball rolling machine, and while rolling, the first modified organic polymer, the second modified organic polymer, and 500g of pseudoboehmite powder (specific surface area 310m²) were added evenly. 2 450g of an organic polymer aqueous solution (with a pore volume of 0.9mL / g) and heat-treated organic polymer were combined and spheroidized to obtain material B. Material B was then subjected to low-temperature heat treatment at 200℃ for 4h to obtain material C. 298mL of an aqueous solution containing 35.35g of ferric nitrate was added to material C, and the mixture was dried at 90℃ for 8h, followed by calcination at 700℃ for 3h under a nitrogen atmosphere to obtain spherical carriers with a particle size of 0.5~0.8mm. The carrier yield and wear data are shown in Table 1.

[0077] (2) Catalyst preparation

[0078] Dissolve 6.99 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 19.00 g of molybdenum trioxide and 8.39 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and make up to 85 mL to obtain Mo-Ni-P aqueous solution.

[0079] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 550℃ for 3h to obtain the catalyst, in which the content of MoO3 was 15.0wt%, the content of NiO was 3.75wt%, and the content of P was 1.5wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0080] (3) Catalyst evaluation

[0081] The catalyst was evaluated over a long period using a CSTR hydrogenation evaluation system, with an operating time of 1200 hours. The evaluation conditions were: reaction temperature 400℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.4 h⁻¹. -1 The hydrogen-to-oil volume ratio was 600:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0082] Example 3

[0083] (1) Carrier preparation

[0084] Weigh 80g of corn starch and add it to 2000g of water. Heat at 70℃ for 20 minutes to obtain a heat-treated aqueous solution of organic polymer. Add 600g of amorphous aluminum silica (specific surface area 290 μm). 2 540g of a heated organic polymer aqueous solution (with a pore volume of 0.85mL / g) and 56g of corn starch, 56g of citric acid, and 190g of water were mixed and heated to 40℃ for 3 hours. The mixture was then filtered, washed, and dried at 40℃ for 24 hours to obtain the first modified organic polymer. 42.0g of corn starch was mixed with 40g of 10wt% ammonia water to obtain the second modified organic polymer. Material A was placed in a ball rolling machine, and while rolling, the first modified organic polymer, the second modified organic polymer, and 400g of pseudoboehmite powder (specific surface area 310m²) were uniformly added. 2 360g of an organic polymer aqueous solution (with a pore volume of 0.9mL / g) and heat-treated ferric nitrate were combined and spheroidized to obtain material B. Material B was then subjected to low-temperature heat treatment at 200℃ for 4h to obtain material C. 240mL of an aqueous solution containing 28.28g of ferric nitrate was added to material C, and the mixture was dried at 90℃ for 8h, followed by calcination at 750℃ for 3h under a nitrogen atmosphere to obtain spherical carriers with a particle size of 0.5~0.8mm. The carrier yield and wear data are shown in Table 1.

[0085] (2) Catalyst preparation

[0086] Dissolve 6.99 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 19.00 g of molybdenum trioxide and 8.39 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and make up to 85 mL to obtain Mo-Ni-P aqueous solution.

[0087] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 550℃ for 3h to obtain the catalyst, which contained 15.0wt% MoO3, 3.75wt% NiO, and 1.5wt% P. 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 .

[0088] (3) Catalyst evaluation

[0089] The catalyst was evaluated over a long period using a CSTR hydrogenation evaluation system, with an operating time of 1200 hours. The evaluation conditions were: reaction temperature 400℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.4 h⁻¹. -1 The hydrogen-to-oil volume ratio was 600:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0090] Example 4

[0091] The preparation was essentially the same as in Example 3, except that corn starch was replaced with potato starch to obtain a spherical support with a particle size of 0.5~0.8 mm. The support yield and wear data are shown in Table 1. A catalyst was prepared, in which the content of MoO3 was 15.0 wt%, the content of NiO was 3.75 wt%, and the content of P was 1.5 wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0092] The catalyst was evaluated in the same way 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 5

[0094] The preparation was essentially the same as in Example 3, except that 80g of corn starch was replaced with 67.41g of methylcellulose, 56g of corn starch with 47.19g of methylcellulose, and 42g of corn starch with 35.39g of methylcellulose, to obtain spherical supports with a particle size of 0.5~0.8mm. The support yield and wear data are shown in Table 1. A catalyst was prepared, containing 15.0wt% MoO3, 3.75wt% NiO, and 1.5wt% P. The physicochemical properties of the catalyst are shown in Table 2.

[0095] The catalyst was evaluated in the same way 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] Example 6

[0097] (1) Carrier preparation

[0098] The method is basically the same as Example 3, except that 56g of citric acid and 190g of water are replaced with 190g of 15% hydrochloric acid aqueous solution, 28.28g of ferric nitrate is replaced with 18.41g of ferric acetate, and the 0.5~0.8mm spherical carrier is replaced with a 1.2~1.5mm spherical carrier. The carrier yield and wear data are shown in Table 1.

[0099] (2) Catalyst preparation

[0100] Dissolve 10.18 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 12.14 g of molybdenum trioxide and 10.18 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and bring the volume to 85 mL to obtain the Mo-Ni-P aqueous solution.

[0101] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 550℃ for 3h to obtain the catalyst, which contained 20.0wt% MoO3, 5.0wt% NiO, and 2.0wt% P. The physicochemical properties of the catalyst are shown in Table 2.

[0102] The catalyst was evaluated in the same way 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.

[0103] Comparative Example 1

[0104] (1) Carrier preparation

[0105] Weigh 80g of corn starch and add it to 2000g of water. Heat at 70℃ for 20 minutes to obtain a heat-treated aqueous solution of organic polymer. Add 400g of amorphous aluminum silica (specific surface area 290m²) to the solution. 2 14.4g of corn starch and 360g of water were mixed and spherical to obtain spherical material A. 42g of corn starch, 42g of citric acid, and 140g of water were mixed and heated to 40℃ for 3 hours, then filtered and washed with water, and dried at 40℃ for 24 hours to obtain the first modified organic polymer. 21.0g of corn starch was mixed with 20g of 10wt% ammonia water to obtain the second modified organic polymer. Material A was placed in a ball rolling machine, and while rolling, the first modified organic polymer, the second modified organic polymer, and 600g of pseudoboehmite powder (specific surface area 310m²) were uniformly added. 2 Material B was obtained by pelletizing 21.6 g of corn starch (with a pore volume of 0.9 mL / g) and 540 g of water. Material B was then subjected to low-temperature heat treatment at 200℃ for 4 h to obtain material C. 360 mL of an aqueous solution containing 42.42 g of ferric nitrate was added to material C, and the mixture was dried at 90℃ for 8 h, followed by calcination at 650℃ for 3 h under a nitrogen atmosphere to obtain spherical carriers with a particle size of 0.5–0.8 mm. The carrier yield and wear data are shown in Table 1.

[0106] (2) Catalyst preparation

[0107] Dissolve 6.99 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 19.00 g of molybdenum trioxide and 8.39 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and make up to 85 mL to obtain Mo-Ni-P aqueous solution.

[0108] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 550℃ for 3h to obtain the catalyst, in which the content of MoO3 was 15.0wt%, the content of NiO was 3.75wt%, and the content of P was 1.5wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0109] (3) Catalyst evaluation

[0110] The catalyst was evaluated over a long period using a CSTR hydrogenation evaluation system, with an operating time of 1200 hours. The evaluation conditions were: reaction temperature 400℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.4 h⁻¹. -1 The hydrogen-to-oil volume ratio was 600:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0111] Comparative Example 2

[0112] (1) Carrier preparation

[0113] Weigh 80g of corn starch and add it to 2000g of water. Heat at 70℃ for 20 minutes to obtain a heat-treated aqueous solution of organic polymer. Add 400g of amorphous aluminum silica (specific surface area 290m²) to the solution. 2 The mixture of 360g of heated organic polymer aqueous solution (with a pore volume of 0.85mL / g) and corn starch (with a pore volume of 0.85mL / g) was stirred and then spherical to obtain spherical material A. 42g of corn starch and 140g of water were mixed and heated to 40℃ for 3 hours, then filtered and washed, and dried at 40℃ for 24 hours to obtain the first modified organic polymer. 21.0g of corn starch and 20g of water were mixed to obtain the second modified organic polymer. Material A was placed in a ball rolling machine, and while rolling, the first modified organic polymer, the second modified organic polymer, and 600g of pseudoboehmite powder (with a specific surface area of ​​310m²) were uniformly added. 2540g of an organic polymer aqueous solution (with a pore volume of 0.9mL / g) and heat-treated organic polymer were combined and spheroidized to obtain material B. Material B was then subjected to low-temperature heat treatment at 200℃ for 4h to obtain material C. 360mL of an aqueous solution containing 42.42g of ferric nitrate was added to material C, and the mixture was dried at 90℃ for 8h, followed by calcination at 650℃ for 3h under a nitrogen atmosphere to obtain spherical carriers with a particle size of 0.5~0.8mm. The carrier yield and wear data are shown in Table 1.

[0114] (2) Catalyst preparation

[0115] Dissolve 6.99 g of phosphoric acid H3PO4 (concentration 85 wt%) in 80 mL of water, then add 19.00 g of molybdenum trioxide and 8.39 g of basic nickel carbonate, heat to 100 °C and stir under reflux for 2.0 h, filter and make up to 85 mL to obtain Mo-Ni-P aqueous solution.

[0116] The entire Mo-Ni-P aqueous solution was added to 100g of the prepared support, mixed thoroughly, and allowed to stand for 2h. Then, it was dried at 110℃ for 8h and calcined at 550℃ for 3h to obtain the catalyst, in which the content of MoO3 was 15.0wt%, the content of NiO was 3.75wt%, and the content of P was 1.5wt%. The physicochemical properties of the catalyst are shown in Table 2.

[0117] (3) Catalyst evaluation

[0118] The catalyst was evaluated over a long period using a CSTR hydrogenation evaluation system, with an operating time of 1200 hours. The evaluation conditions were: reaction temperature 400℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.4 h⁻¹. -1 The hydrogen-to-oil volume ratio was 600:1. The properties of the feedstock oil used are shown in Table 3, and the evaluation results are shown in Table 4.

[0119] Table 1 Carrier yield and wear

[0120]

[0121] Table 2 Physicochemical properties of catalysts

[0122]

[0123] Table 3 Crude Oil Properties and Evaluation Conditions

[0124]

[0125] Table 4 Catalyst Evaluation Results

[0126]

[0127] With the activity of Comparative Example 1 as 100, the evaluation results of the other activities compared with the Comparative Example are shown in Table 4.

Claims

1. A method for preparing a hydrocracking catalyst, the method comprising the following steps: (1) Under contact conditions, the organic polymer aqueous solution after heat treatment is mixed with amorphous silicon aluminum, and then spherical material A is obtained after molding treatment; (2) The organic polymer is added to an acidic solution for a first modification treatment, and the first modified organic polymer is obtained after the treatment; (3) The organic polymer is added to an aqueous solution of a nitrogen-containing weak alkaline compound for a second modification treatment, and the modified organic polymer is obtained after the treatment; the nitrogen-containing weak alkaline compound is selected from at least one of ammonia, ammonium carbonate and ammonium bicarbonate; (4) Under the rolling ball forming condition, material A is placed in the ball rolling machine, and while rolling, the first modified organic polymer obtained in step (2), the second modified organic polymer obtained in step (3), pseudoboehmite powder and the organic polymer aqueous solution after heat treatment are uniformly introduced, and material B is obtained after treatment. (5) Material B is subjected to low-temperature heat treatment to obtain material C; the low-temperature heat treatment temperature is 100-300℃; (6) Mix material C with an iron-containing compound, and after uniform mixing, dry and calcine to obtain a carrier; (7) After introducing the hydrogenation metal component onto the support obtained in step (6), the catalyst is dried and calcined to obtain a hydrocracking catalyst; the hydrogenation metal component is at least one of Group VIB metals and at least one of Group VIII metals. in, The organic polymer is one or more of starch, cellulose ether, and flour; The preparation process of the organic polymer aqueous solution after heat treatment in steps (1) and (4) is as follows: under heat treatment conditions, the organic polymer is mixed with water until the organic polymer dissolves, and then the organic polymer aqueous solution after heat treatment is obtained. The heat treatment temperature is 60-100℃ and the heat treatment time is 10-40 minutes.

2. The method for preparing the hydrocracking catalyst according to claim 1, wherein, The properties of amorphous silicon-aluminum in step (1) are as follows: specific surface area is 250-320 m². 2 / g, pore volume is 0.7~1.0mL / g, and silica content is 10wt%~50wt%.

3. The method for preparing the hydrocracking catalyst according to claim 1, wherein, The organic polymer is starch.

4. The method for preparing the hydrocracking catalyst according to claim 1, wherein, Starch is derived from 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; cellulose ether is derived from at least one of methylcellulose, hydroxyethyl methylcellulose, carboxymethylcellulose, ethylcellulose, benzylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, cyanoethylcellulose, benzyl cyanoethylcellulose, carboxymethyl hydroxyethylcellulose, and phenylcellulose.

5. The method for preparing the hydrocracking catalyst according to claim 1, wherein, The starch is corn starch and / or potato starch; the cellulose ether is methylcellulose.

6. The method for preparing the hydrocracking catalyst according to claim 1, wherein, The mass concentration of the organic polymer aqueous solution after heat treatment in steps (1) and (4) is 0.5% to 8.0%.

7. The method for preparing the hydrocracking catalyst according to claim 1, wherein, The mass concentration of the organic polymer aqueous solution after heat treatment in steps (1) and (4) is 1.0% to 5.0%.

8. The method for preparing the hydrocracking catalyst according to claim 1, wherein, In step (2), the organic polymer is added to an acidic solution for the first modification treatment. After the treatment is completed, it is cooled, optionally washed with water, and dried to obtain the first modified organic polymer. The acidic solution is an inorganic acid and / or an organic acid, wherein the inorganic acid is selected from one or more of hydrochloric acid, sulfuric acid and nitric acid; and the organic acid is selected from one or more of citric acid, acetic acid, malic acid, lactic acid and tartaric acid.

9. The method for preparing the hydrocracking catalyst according to claim 8, wherein, The inorganic acid is hydrochloric acid; the organic acid is citric acid.

10. The method for preparing the hydrocracking catalyst according to claim 1, wherein, The temperature of the first modification treatment in step (2) is 30-50℃; the time of the first modification treatment is 2-6 hours.

11. The method for preparing the hydrocracking catalyst according to claim 1, wherein, The nitrogen-containing weakly basic compound in step (3) is ammonia.

12. The method for preparing the hydrocracking catalyst according to claim 1, wherein, The amount of the first modified organic polymer added in step (4) is 10wt% to 20wt% of the dry basis mass of the pseudoboehmite powder.

13. The method for preparing the hydrocracking catalyst according to claim 1, wherein, The amount of the second modified organic polymer added in step (4) is 5 wt% to 15 wt% of the dry basis mass of the pseudoboehmite powder.

14. The method for preparing the hydrocracking catalyst according to claim 1, wherein, The amount of the organic polymer aqueous solution added in step (4) after heat treatment is 0.8 to 1.5 times the mass ratio of the pseudoboehmite powder.

15. The method for preparing the hydrocracking catalyst according to claim 1, wherein, The low-temperature heat treatment temperature in step (5) is 150-250℃; the low-temperature heat treatment time is 3-12 hours.

16. The method for preparing the hydrocracking catalyst according to claim 1, wherein, The iron-containing compound in step (6) is a soluble iron salt, which is selected from one or more of ferric nitrate, ferric chloride, ferric acetate and ferric sulfate.

17. The method for preparing the hydrocracking catalyst according to claim 1, wherein, The calcination in step (6) is carried out in the presence of an inert atmosphere, which is one or more of nitrogen, helium, neon, argon, krypton and xenon; the calcination temperature is 600-800℃.

18. The method for preparing the hydrocracking catalyst according to claim 1, wherein, Group VIII metals are Ni and / or Co, and Group VIB metals are W and / or Mo.

19. The method for preparing the hydrocracking catalyst according to claim 1, wherein, The drying temperature in step (7) is 80-140℃; the drying time is 4-12 hours.

20. The method for preparing the hydrocracking catalyst according to claim 1, wherein, The roasting temperature in step (7) is 400-600℃ and the roasting time is 1-5 hours; the roasting is carried out in the presence of an oxygen-containing atmosphere.

21. A hydrocracking catalyst obtained by the preparation method according to any one of claims 1-20.

22. The hydrocracking catalyst according to claim 21, wherein, The carrier is an amorphous silica-alumina and alumina composite carrier with a spherical core-shell structure. The core layer is amorphous silica-alumina, and the shell layer is alumina with a two-level distribution of mesopores and macropores. Based on the weight of the carrier, the content of amorphous silica-alumina in the core layer is 30% to 70%, and the content of alumina in the shell layer is 30% to 70%.

23. The hydrocracking catalyst according to claim 21, wherein, The properties of hydrocracking catalysts are as follows: specific surface area of ​​150–220 m². 2 / g, with a pore volume of 0.40~0.90mL / g, the proportion of mesopores with a pore size of 10~50nm to the total pore volume is 60%~90%, and the proportion of macropores with a pore size greater than 50nm to the total pore volume is 5%~10%.

24. The use of the hydrocracking catalyst according to any one of claims 21-23 in the process of hydrotreating hydrocarbon oils.

25. A crude oil fluidized bed hydrotreating process, wherein crude oil and hydrogen are mixed and then fed into a fluidized bed reactor for hydrotreating, wherein the fluidized bed reactor is filled with the hydrocracking catalyst as described in any one of claims 21-23.

Images