A heavy oil hydroprocessing catalyst, its preparation method and use

Abstract

The present application provides a heavy oil hydrogenation catalyst, a preparation method and application thereof. The preparation method comprises the following steps: preparing a carrier precursor; mixing the obtained carrier precursor with an additive, then adding a solution containing active metals to knead, and then drying and calcining to obtain a catalyst precursor; introducing an active metal component to the obtained catalyst precursor, and then drying and calcining to obtain the heavy oil hydrogenation catalyst. The heavy oil hydrogenation catalyst provided by the present application has suitable acidity, pore structure, hydrogenation activity and mechanical properties, and is particularly suitable for a boiling bed heavy oil hydrogenation process. The preparation method of the hydrogenation catalyst is simple, has low energy consumption, and is suitable for large-scale production.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of petroleum chemical industry, and relates to a catalytic material and a preparation method thereof, in particular to a heavy oil hydrogenation catalyst and a preparation method thereof. BACKGROUND

[0002] In the face of the increasing demand for clean fuel and chemical raw materials, and the situation that the properties of crude oil are becoming heavier and poorer, heavy oil hydrogenation technology is paid more and more attention by researchers. In the residue hydrocracking, the catalyst usually needs appropriate acidity for mild cracking, mesopore for diffusion of large molecules such as asphaltene to active sites, and high hydrogenation activity to avoid coking. The macroporous pseudo-boehmite is usually used as the raw material of the residue hydrocracking catalyst carrier, but the macroporous pseudo-boehmite prepared by the current pseudo-boehmite production process has weak acidity, low peptization index and poor cohesiveness, so that when used as a hydroprocessing catalyst material, the hydrogenation activity of the catalyst is low, and the mechanical strength is also not high.

[0003] CN104646070A discloses a preparation method of a supported hydroprocessing catalyst carrier, which enhances the strength of the catalyst carrier by using high-concentration organic acid as a binder to enhance the binding force between the catalyst carriers. This method uses high-concentration organic acid instead of traditional nitric acid to reduce NOx emissions during the calcination process, but still needs to add high-concentration acid during the preparation of the carrier.

[0004] CN104096584A discloses a residue hydrocracking catalyst and a preparation method thereof, which introduces a small amount of activated carbon into alumina to reduce the reaction between Ni2P active components and alumina during the generation process, and improve the dispersion, so as to fully exert the high activity of Ni2P and the carrier advantage of the alumina-activated carbon kneaded body, and further improve the impurity removal capacity of the catalyst such as desulfurization and carbon residue.

[0005] CN113578337A discloses a residue hydrocracking catalyst and a preparation method and application thereof, which obtains a catalyst carrier with a directional arrangement of pore structures by molding and crushing magnesium oxide and alumina, improves the demetallization and anti-coking capacity of the catalyst, and increases the acid center of the catalyst carrier by acid treatment. SUMMARY

[0006] In view of the deficiencies of the prior art, the present application provides a heavy oil hydrogenation catalyst and a preparation method and application thereof. The heavy oil hydrogenation catalyst provided by the present application has appropriate acidity, pore structure, hydrogenation activity and mechanical properties, and is particularly suitable for the ebullated bed heavy oil hydrogenation process. The preparation method of the hydrogenation catalyst is simple, low in energy consumption, and suitable for large-scale production.

[0007] (I) The present application provides a preparation method of a heavy oil hydrogenation catalyst, the preparation method comprising the following steps:

[0008] S1: preparing a carrier precursor;

[0009] S2: mixing the carrier precursor obtained in step S1 with an additive, then adding a solution containing active metals for kneading, and then obtaining a catalyst precursor after first drying and first calcination;

[0010] S3: introducing an active metal component to the catalyst precursor obtained in step S2, and then obtaining a heavy oil hydrogenation catalyst after second drying and second calcination.

[0011] In the preparation method of the heavy oil hydrogenation catalyst, in some specific embodiments, the carrier precursor preparation method comprises the following steps:

[0012] (1) preparing a sol: uniformly mixing a silicon source A, a template agent and water to obtain a sol;

[0013] (2) uniformly mixing the sol obtained in step (1) with alcohol and then performing heat treatment, and obtaining a stream A after the treatment;

[0014] (3) adding a silicon source B, an acidic aluminum source and an alkaline aluminum source into a reactor containing bottom water, obtaining a stream B after the reaction, and then uniformly mixing with a non-ionic surfactant to obtain a stream C;

[0015] (4) hydrothermally treating the stream C under hydrothermal treatment conditions, and then obtaining a carrier precursor after washing and drying.

[0016] In the preparation method of the heavy oil hydrogenation catalyst, in some specific embodiments, the silicon source A in step (1) is one or more of tetraethyl orthosilicate, tetramethyl orthosilicate and silica sol, and is preferably tetraethyl orthosilicate.

[0017] In the preparation method of the heavy oil hydrogenation catalyst, in some specific embodiments, the template agent in step (1) is tetrapropylammonium hydroxide and / or tetrapropylammonium bromide; and is preferably tetrapropylammonium hydroxide.

[0018] In the preparation method of the heavy oil hydrogenation catalyst, in some specific embodiments, the alcohol in step (2) is C1-C3 alcohol, which can be one or more of monohydric alcohol, dihydric alcohol and polyhydric alcohol; and the specific alcohol can be one or more of ethanol, ethylene glycol and glycerol, and is preferably glycerol.

[0019] In the preparation method of the heavy oil hydrogenation catalyst, in some specific embodiments, the amount of the silicon source A, the template agent, water and alcohol is (3-6):(5-8):(2-4):(0.5-5) by weight.

[0020] In some embodiments of the preparation method of the heavy oil hydro- treating catalyst, the heat treatment operation conditions in step (2) are as follows: the treatment temperature is 60-100°C, and the treatment time is not more than 24 hours; preferably, the treatment temperature is 80-100°C, and the treatment time is 8-12 hours.

[0021] In some embodiments of the preparation method of the heavy oil hydro- treating catalyst, the silicon source B in step (3) is water glass and / or alkaline silica sol, preferably alkaline silica sol.

[0022] In some embodiments of the preparation method of the heavy oil hydro- treating catalyst, the acidic aluminum source in step (3) is a water-soluble acidic aluminum- containing compound, preferably a water-soluble acidic inorganic aluminum- containing compound, in particular a water-soluble inorganic strong acid aluminum salt, more preferably selected from one or more of aluminum sulfate, aluminum nitrate, and aluminum chloride, preferably aluminum sulfate.

[0023] In some embodiments of the preparation method of the heavy oil hydro- treating catalyst, the basic aluminum source in step (3) is an aluminite solution of an alkali metal; specifically, selected from one or more of sodium aluminite and potassium aluminite, preferably sodium aluminite.

[0024] In some embodiments of the preparation method of the heavy oil hydro- treating catalyst, the pH value of the stream B in step (3) is 4-7, preferably 5-6; the pH value of the stream B is regulated by the amount of the acidic aluminum source.

[0025] In some embodiments of the preparation method of the heavy oil hydro- treating catalyst, the reaction temperature in step (3) is 50-90°C, preferably 50-80°C.

[0026] In some embodiments of the preparation method of the heavy oil hydro- treating catalyst, the aluminum content of the acidic aluminum source in step (3) is 10-70 g Al2O3 / L, the aluminum content of the basic aluminum source is 70-170 g Al2O3 / L, and the silicon content of the second silicon source is 20-80 g SiO2 / L.

[0027] In some embodiments of the preparation method of the heavy oil hydro- treating catalyst, the amount of water in step (3) is 10%-20% of the total volume of the reaction system, preferably 13%-20%.

[0028] In some embodiments of the preparation method of the heavy oil hydroprocessing catalyst, the non-ionic surfactant in step (3) is one or more of polyethylene glycol, alkyl alcohol amide, polyether, preferably polyethylene glycol, the alkyl alcohol amide is one or more of lauramide diethanolamine, coconut oil fatty acid diethanolamide, and the polyether is one or more of AEO-6 and AEO-9; the molecular weight of the polyethylene glycol is 200-1000, preferably 200-700.

[0029] In some embodiments of the preparation method of the heavy oil hydroprocessing catalyst, the weight ratio of the stream A obtained in step (2) to the stream C in step (3) is 1:80-100.

[0030] In some embodiments of the preparation method of the heavy oil hydroprocessing catalyst, the hydrothermal treatment conditions in step (4) are as follows: the treatment temperature is 100-180°C, preferably 110-160°C, and more preferably 120-150°C; the treatment pressure is 0.1-0.5 MPa, preferably 0.1-0.3 MPa; and the treatment time is 0.5-10 h, preferably 0.5-6 h.

[0031] In some embodiments of the preparation method of the heavy oil hydroprocessing catalyst, the washing in step (4) is washing with water, the washing temperature is 70-90°C, and the washing is repeated several times until the liquid is neutral.

[0032] In some embodiments of the preparation method of the heavy oil hydroprocessing catalyst, the drying conditions in step (4) are as follows: the drying temperature is 100-150°C, and the drying time is 6-10 h.

[0033] In some embodiments of the preparation method of the heavy oil hydroprocessing catalyst, the additive in step S2 is one or more of methyl cellulose, hydroxymethyl cellulose, and hydroxypropyl methyl cellulose, and the content of the additive is 0.5-5 wt% based on the mass of the carrier precursor.

[0034] In some embodiments of the preparation method of the heavy oil hydroprocessing catalyst, after mixing in step S2, the mixture can be first shaped and then dried and calcined, and the shaping can be performed by using the existing shaping methods in the art, and the shaped product can be in the shape of a cylindrical bar, a sphere, a toothed sphere, or a multi-leaf grass type.

[0035] In some embodiments of the preparation method of the heavy oil hydroprocessing catalyst, the first drying conditions in step S2 are as follows: the first drying temperature is 90-120°C, and the first drying time is 2-10 h.

[0036] In some embodiments of the preparation method of the heavy oil hydroprocessing catalyst, the first calcination conditions in step S2 are as follows: the first calcination temperature is 500-800°C, and the first calcination time is 4-10h.

[0037] In some embodiments of the preparation method of the heavy oil hydroprocessing catalyst, the active metal in step S2 is one or more of Group VIB metal and / or Group VIII metal. The concentration of the solution containing the active metal and the amount of the solution are such that the content of Group VIII metal in the final catalyst precursor is 0.5-5wt%, preferably 1.0-3.0wt%, and the content of Group VIB metal is 1.0-10.0wt%, preferably 2.0-5.0wt%. The Group VIII metal is one or more of Ni and Co, and the Group VIB metal is one or more of Mo and W. The precursor containing the active metal component, water, and optionally a phosphorus-containing compound are mixed uniformly to obtain the solution containing the active metal.

[0038] In some embodiments of the preparation method of the heavy oil hydroprocessing catalyst, the method for introducing the active metal component in step S3 can use one of the existing methods such as impregnation and kneading, and preferably uses the impregnation method. When the impregnation method is used to load the active metal component, the existing impregnation method in the art can be used, and the spray impregnation method, the saturated impregnation method, or the supersaturated impregnation method can be used. When the impregnation method is used, the precursor containing the active metal component, water, and optionally a phosphorus-containing compound are first mixed uniformly to obtain the solution containing the active metal, and then the carrier is mixed uniformly, followed by standing, drying, and calcination to obtain the catalyst.

[0039] In some embodiments of the preparation method of the heavy oil hydroprocessing catalyst, the precursor containing the active metal component is a compound containing Group VIB metal and / or 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 trioxide 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 can be one or more of phosphoric acid, ammonium dihydrogen phosphate, and ammonium monohydrogen phosphate.

[0040] In some embodiments of the preparation method of the heavy oil hydroprocessing catalyst, in step S3, the hydrogenation active metal component is one or more of Group VIB metal and / or Group VIII metal, the concentration of the compound containing hydrogenation active metal in the solution and the amount of the solution are such that the content of Group VIII metal in the final catalyst is 1.5-10.0 wt%, preferably 2.0-8.0 wt%, and the content of Group VIB metal is 5.0-25.0 wt%, preferably 10.0-20.0 wt%. The Group VIII metal is one or more of Ni and Co, and the Group VIB metal is one or more of Mo and W.

[0041] In some embodiments of the preparation method of the heavy oil hydroprocessing catalyst, in step S3, the second drying condition includes that the second drying temperature is 90-120°C, and the second drying time is 2-10 h.

[0042] In some embodiments of the preparation method of the heavy oil hydroprocessing catalyst, in step S3, the second calcination condition includes that the second calcination temperature is 300-600°C, and the second calcination time is 4-10 h.

[0043] The second aspect of the present application provides a heavy oil hydroprocessing catalyst prepared by the above method.

[0044] Further, in the heavy oil hydroprocessing catalyst, as one embodiment, the hydrogenation catalyst comprises a carrier and an active metal component, the carrier is a silicon-aluminum material, and the metal element in the active metal component is at least one of Group VIII metal and Group VIB metal, the Group VIII metal is one or more of Ni and Co, and the Group VIB metal is one or more of Mo and W.

[0045] Further, in the heavy oil hydroprocessing catalyst, as one embodiment, the content of Group VIII metal is 1.5-10.0 wt% in terms of oxide, preferably 2.0-8.0 wt%, and the content of Group VIB metal is 5.0-25.0 wt% in terms of oxide, preferably 10.0-20.0 wt%, based on the total weight of the hydrogenation catalyst.

[0046] Further, in the heavy oil hydroprocessing catalyst, as one embodiment, the hydrogenation catalyst has the following properties: pore volume is 0.50-0.80 mL / g, specific surface area is 150-280 m 2 / g.

[0047] Further, in the heavy oil hydroprocessing catalyst, as a specific embodiment, the pore distribution of the catalyst has the following characteristics: the pore volume of the pores with a pore diameter of 8-20 nm accounts for 40%-70% of the total pore volume, and the pore volume of the pores with a pore diameter >100 nm accounts for more than 10% of the total pore volume.

[0048] Further, in the heavy oil hydroprocessing catalyst, as a specific embodiment, the catalyst has a diameter of less than 1.5 mm and a side pressure strength of more than 10 N / mm.

[0049] The application further provides a use of the heavy oil hydroprocessing catalyst in a heavy oil hydroprocessing reaction.

[0050] Further, in the use, the heavy oil can be at least one or more of atmospheric residue, vacuum residue, catalytic slurry oil, and coal tar.

[0051] Further, in the use, the hydroprocessing reaction conditions are generally as follows: a reaction temperature of 320-520 ℃, a reaction pressure of 8-20 MPa, a liquid hourly space velocity of 0.1-0.5 h -1 , and a hydrogen / oil volume ratio of 300-1000.

[0052] Further, in the use, the heavy oil hydroprocessing reaction is carried out in a fixed bed reactor, a boiling bed reactor, or a suspended bed hydroprocessing reactor, and is preferably carried out in a boiling bed hydroprocessing reactor.

[0053] The heavy oil hydroprocessing catalyst and the preparation method thereof provided by the application have the following technical effects and advantages compared with the prior art:

[0054] 1. The heavy oil hydroprocessing catalyst provided by the application uses a silicon-aluminum material as a carrier, and has high side pressure strength, good wear resistance, good mechanical properties, and can provide strong B acid for the catalyst, which is beneficial to the hydroprocessing of residue oil.

[0055] 2. In the preparation method of the heavy oil hydroprocessing catalyst, the introduction of the additive enhances the binding force between the catalyst carriers and the strength of the catalyst carriers. Meanwhile, the active metal components are introduced in two steps, which is more conducive to reducing the agglomeration between the metals, improving the dispersion of the metals, and increasing the active centers on the surface of the catalyst.

[0056] 3. In the preparation method of the heavy oil hydroprocessing catalyst, the silicon-aluminum material used as the carrier precursor has a large pore volume, a mesopore-macropore two-stage gradient pore channel, and a molecular sieve property, and has the characteristics of high B acid content of the molecular sieve and low impurity content (especially low sodium content), and is particularly suitable for being used as a carrier of a heavy oil hydroprocessing catalyst.

[0057] 4、The preparation method of the heavy oil hydrogenation catalyst in the application, in the preparation process of the carrier precursor, when the semi-crystallized precursor is prepared, the over-crystallization of the precursor is regulated by adding a non-ionic surfactant, then the precursor is added into the silicon-aluminum material, so that the silicon-aluminum material grows on the surface of the precursor to form a high surface acidity and a hierarchical pore structure of mesopore-macropore. At the same time, the precursor provides crystal nuclei for the subsequent reaction, and the acidified silica gel and aluminum hydroxide colloid are adsorbed on the crystal nuclei formed by the precursor, which promotes the increase of the grain size of the prepared silicon-aluminum material, and is beneficial to the formation of a silicon-aluminum material with a large pore volume, a large pore size and strong acidity.

[0058] 5、The preparation method of the heavy oil hydrogenation catalyst in the application, in the preparation process of the carrier precursor, a non-ionic surfactant is added, so that the soluble silicon species in the slurry exchanges with the like ions on the surface of the non-ionic surfactant micelles and is adsorbed on the surface of the micelles, and also interacts with the non-ionic surfactant molecules in the liquid phase to form new inorganic-organic complexes. The adsorbed micelles and complex molecules with silicon species are formed into mesoporous materials with stable structures at a lower temperature under the action of ionic bonds, hydrogen bonds and intermolecular dispersion forces through multiple thermodynamic equilibria. DETAILED DESCRIPTION

[0059] The technical solutions of the application are further described below by examples and comparative examples, but are not limited to the following examples.

[0060] In the context of the present specification, the pore volume, specific surface area and pore size distribution are measured by low-temperature nitrogen adsorption method. The total acid, B acid and L acid are measured by pyridine infrared adsorption method.

[0061] In the context of the present specification, the lateral strength is measured by a strength meter using the Q / SH 361 926-2020 method.

[0062] In the context of the present specification, the metal dispersion is determined by X-ray photoelectron spectroscopy analysis (XPS) method. The X-ray photoelectron spectroscopy analysis (XPS) uses Shimadzu AXIS SPURA+, and all binding energies are corrected with contaminant carbon (C1s 284.8 eV). Al Ka photoelectron source, E b = 1486.6 eV.

[0063] In the absence of explicit indications, all percentages, parts, ratios, etc. mentioned in the present specification are by weight, and the pressure is gauge pressure.

[0064] In the context of the present specification, any two or more embodiments of the application can be combined arbitrarily, and the technical solutions formed thereby belong to the part of the original disclosure of the present specification and also fall within the protection scope of the application.

[0065] Example 1

[0066] (1) Preparation of the silica-alumina material

[0067] An aluminum sulfate solution with a concentration of 50 g Al203 / L and a silica sol solution with a concentration of 60 g Si02 / L were prepared and kept ready for use. A sodium metaaluminate solution with a caustic ratio of 1.20 and a concentration of 150 g Al203 / L was prepared and kept ready for use. A sol was prepared by mixing 50 g tetraethyl orthosilicate (TEOS), 70 g tetrapropylammonium hydroxide (TPAOH) and 30 g deionized water, and then the mixture was stirred with 15 g glycerol at 60°C for 18 h to obtain a precursor solution. 500 mL of deionized water was added to a 5000 mL reactor as a bottom water, and stirring was started and heating was initiated. After the deionized water was heated to 65°C, the prepared aluminum sulfate solution was added to the reactor at a rate of 16 mL / min, and the prepared sodium metaaluminate and silica sol were added in a concurrent flow. The pH of the reaction was controlled at 7.0 by adjusting the flow rates of the sodium metaaluminate and silica sol, and the temperature and pH of the slurry in the reactor were kept constant. After the reaction was completed, 20 g of polyethylene glycol 200 was added to the reactor under stirring conditions, and then 40 g of the precursor solution was added to the above solution and stirred until it was uniformly mixed. The slurry was placed in the reactor, and the treatment was carried out at a temperature of 100°C and a pressure of 0.2 MPa for 8 h under stirring conditions. The treated slurry was washed with hot water at 90°C until the liquid was neutral, and then dried at 150°C for 6 h to obtain a support precursor.

[0068] (2) Preparation of the catalyst

[0069] Molybdenum oxide (content 99%) 53.29 g, basic nickel carbonate (nickel oxide content 54 wt%) 24.42 g, and phosphoric acid 19.62 g were weighed and heated to prepare an impregnation solution of 500 mL. The support precursor 400 g (dry basis 70 wt%) and methyl cellulose 2.8 g were mixed, 100 mL of the above impregnation solution was diluted ten times, and then added to the mixture and kneaded. After extrusion and molding, the hydrogenation catalyst support was obtained by drying at 110°C for 6 h and calcining at 700°C for 4 h. The hydrogenation catalyst A was obtained by impregnating the support using the equal volume impregnation method, drying at 100°C for 10 h, and calcining at 500°C for 3 h. The physicochemical properties of the obtained catalyst are listed in Table 1.

[0070] Example 2

[0071] (1) Preparation of the silica-alumina material

[0072] An aluminum chloride solution with a concentration of 30 g Al203 / L and a water glass solution with a concentration of 30 g Si02 / L and a modulus of 2.5 were prepared and kept ready for use. A sodium metaaluminate solution with a caustic ratio of 1.20 and a concentration of 100 g Al203 / L was prepared and kept ready for use. A sol was prepared by stirring together 60 g of methyl orthosilicate, 80 g of tetrapropylammonium hydroxide (TPAOH) and 40 g of deionized water, and then mixing the sol with 50 g of ethanol and aging the mixture at 80°C for 8 h to obtain a precursor solution. A 5000 mL reactor was charged with 700 mL of deionized water as a bottom water, and stirring was started and heating was initiated. After the deionized water was heated to 70°C, the prepared aluminum chloride solution was added to the reactor at a rate of 14 mL / min, and the prepared sodium metaaluminate and water glass were added concurrently. The pH of the reaction was controlled at 6.0 by adjusting the flow rates of the sodium metaaluminate and water glass, and the temperature and pH of the slurry in the reactor were kept constant. After the reaction was completed, 10 g of lauryl diethanolamide was added to the reactor under stirring conditions, and then 45 g of the precursor solution was added to the above solution and stirred until the mixture was homogeneous. The slurry was placed in the reactor, and the slurry was treated at a temperature of 120°C and a pressure of 0.2 MPa for 4 h under stirring conditions. The treated slurry was washed with hot water at 70°C until the liquid was neutral, and then the slurry was dried at 120°C for 8 h to obtain a support precursor.

[0073] (2) Catalyst preparation

[0074] Molybdenum oxide (content 99%) 38.86 g, basic nickel carbonate (content of nickel oxide 54 wt%) 17.81 g, and phosphoric acid 17.88 g were weighed out and heated to prepare an impregnation solution of 500 ml. The support precursor 400 g (dry basis 70 wt%) and hydroxymethyl cellulose 11.2 g were mixed, 100 ml of the above impregnation solution was diluted ten times, and then the mixture was added and kneaded, and then extruded into a strip, and then dried at 100°C for 6 h and calcined at 600°C for 6 h to obtain a hydrogenation catalyst support. The support was impregnated by the equal volume impregnation method, and then dried at 110°C for 8 h and calcined at 600°C for 3 h to obtain a hydrogenation catalyst B. The physicochemical properties of the obtained catalyst are listed in Table 1.

[0075] Example 3

[0076] (1) Preparation of silicon-aluminum material

[0077] An aluminum nitrate solution with a concentration of 70 g Al203 / L and a silica sol solution with a concentration of 80 g Si02 / L were prepared and kept ready for use. A potassium meta-aluminate solution with a concentration of 170 g Al203 / L and a caustic ratio of 1.20 was prepared and kept ready for use. A sol was prepared by stirring 30 g of the silica sol, 50 g of tetrapropylammonium hydroxide (TPAOH) and 20 g of deionized water, and then mixing the sol with 15 g of ethylene glycol and aging at 80°C for 8 h to obtain a precursor solution. 1000 mL of deionized water was added to a 5000 mL reactor as a bottom water, and stirring was started and heating was started. After the deionized water was heated to 70°C, the prepared aluminum nitrate solution was added to the reactor at a rate of 18 mL / min, and the prepared potassium meta-aluminate and silica sol were added in a concurrent flow. The pH of the reaction was controlled to be 6.0 by adjusting the flow rates of the potassium meta-aluminate and silica sol, and the temperature and pH of the slurry in the reactor were kept constant. After the reaction was completed, 10 g of AEO-9 was added to the reactor under stirring conditions, and then 50 g of the precursor solution was added to the above solution and stirred until it was uniformly mixed. The slurry was placed in the reactor, and the treatment was carried out at a temperature of 180°C and a pressure of 0.5 MPa for 0.5 h under stirring conditions. The treated slurry was washed with hot water at 80°C until the liquid was neutral, and then dried at 100°C for 10 h to obtain a support precursor.

[0078] (2) Catalyst preparation

[0079] Molybdenum oxide (content 99%) 186.98 g, nickel carbonate (content of nickel oxide 54 wt%) 68.56 g, phosphoric acid 45.90 g were weighed and prepared into 500 ml of impregnation solution by heating. The support precursor 400 g (dry basis 70 wt%) and hydroxypropyl methyl cellulose 5.6 g were mixed, 100 ml of the above impregnation solution was diluted ten times, and then added to the above mixture and kneaded, and then extruded into a strip, dried at 110°C for 6 h, and calcined at 500°C for 5 h to obtain a hydrogenation catalyst support. The support was impregnated by the equal volume impregnation method, dried at 90°C for 10 h, and calcined at 400°C for 4 h to obtain a hydrogenation catalyst C. The physicochemical properties of the obtained catalyst are listed in Table 1.

[0080] Comparative Example 1

[0081] Molybdenum oxide (content 99%) 186.98 g, nickel carbonate (content of nickel oxide 54 wt%) 68.56 g, phosphoric acid 45.90 g were weighed and prepared into 500 ml of impregnation solution by heating. The support precursor 400 g (dry basis 70 wt%) and hydroxypropyl methyl cellulose 5.6 g were mixed, 100 ml of the above impregnation solution was diluted ten times, and then added to the above mixture and kneaded, and then extruded into a strip, dried at 110°C for 6 h, and calcined at 500°C for 5 h to obtain a hydrogenation catalyst support. The support was impregnated by the equal volume impregnation method, dried at 90°C for 10 h, and calcined at 400°C for 4 h to obtain a hydrogenation catalyst C. The physicochemical properties of the obtained catalyst are listed in Table 1.

[0082] Take 400g of industrial pseudo-boehmite raw material (70wt% on dry basis), mix with 2.8g of methyl cellulose, take 100ml of the above impregnation solution, dilute ten times, then add the above mixture and knead, extrude into strips, dry at 110°C for 6h, and calcine at 700°C for 4h to obtain a hydrogenation catalyst carrier;

[0083] The carrier is impregnated by the equal volume impregnation method, dried at 100°C for 10h, and calcined at 500°C for 3h to obtain hydrogenation catalyst D1. The physicochemical properties of the obtained catalyst are listed in Table 2.

[0084] Comparative Example 2

[0085] The carrier precursor is prepared as in Example 1.

[0086] Take 53.29g of molybdenum oxide (content 99%), 24.42g of basic nickel carbonate (nickel oxide content 54wt%), and 19.62g of phosphoric acid, and heat to prepare 500ml of impregnation solution.

[0087] Take 400g of carrier precursor (70wt% on dry basis), add 2.8g of methyl cellulose and water, knead, extrude into strips, dry at 110°C for 6h, and calcine at 700°C for 4h to obtain a hydrogenation catalyst carrier;

[0088] The carrier is impregnated by the equal volume impregnation method, dried at 100°C for 10h, and calcined at 500°C for 3h to obtain hydrogenation catalyst D2. The physicochemical properties of the obtained catalyst are listed in Table 2.

[0089] Comparative Example 3

[0090] The carrier precursor is prepared as in Example 1.

[0091] Take 53.29g of molybdenum oxide (content 99%), 24.42g of basic nickel carbonate (nickel oxide content 54wt%), and 19.62g of phosphoric acid, and heat to prepare 500ml of impregnation solution.

[0092] Take 400g of carrier precursor (70wt% on dry basis), add 2.8g of methyl cellulose and water, knead, extrude into strips, dry at 110°C for 6h, and calcine at 700°C for 4h to obtain a hydrogenation catalyst carrier;

[0093] The carrier is impregnated by the equal volume impregnation method, dried at 100°C for 10h, and calcined at 500°C for 3h to obtain hydrogenation catalyst D3. The physicochemical properties of the obtained catalyst are listed in Table 2.

[0094] Comparative Example 4

[0095] An aluminum sulfate solution with a concentration of 50 g Al2O3 / L and a silica sol solution with a concentration of 60 g SiO2 / L were prepared and kept ready for use. A sodium metaaluminate solution with a caustic ratio of 1.20 and a concentration of 150 g Al2O3 / L was prepared and kept ready for use. A sol was prepared by mixing 50 g of tetraethyl orthosilicate (TEOS) and 30 g of deionized water, and then the mixture was stirred and aged at 60°C for 18 h to obtain a precursor solution. 500 mL of deionized water was added to a 5000 mL reactor as a bottom water, and stirring was started and heating was started. After the deionized water was heated to 65°C, the prepared aluminum sulfate solution was added to the reactor at a rate of 16 mL / min, and the prepared sodium metaaluminate and silica sol were added in a concurrent flow. The pH of the reaction was controlled to be 7.0 by adjusting the flow rates of the sodium metaaluminate and silica sol, and the temperature and pH of the slurry in the reactor were kept constant. After the reaction was completed, 20 g of polyethylene glycol 200 was added to the reactor under stirring conditions, and then 40 g of the precursor solution was added to the above solution and stirred until the mixture was uniform. The above slurry was placed in the reactor, and the treatment was carried out at a temperature of 100°C, a pressure of 0.2 MPa, and for 8 h under stirring conditions. The treated slurry was washed with hot water at 90°C until the liquid was neutral, and then dried at 150°C for 6 h to obtain a support precursor B-1.

[0096] (2) Catalyst preparation

[0097] Molybdenum oxide (content 99%) 53.29 g, nickel carbonate (content of nickel oxide 54 wt%) 24.42 g, and phosphoric acid 19.62 g were weighed and heated to prepare an impregnation solution of 500 mL. The support precursor B-1 400 g (dry basis 70 wt%) and methyl cellulose 2.8 g were mixed, 100 mL of the above impregnation solution was diluted ten times, and then added to the above mixture and kneaded. After being extruded into a strip, the hydrogenation catalyst support was obtained by drying at 110°C for 6 h and calcining at 700°C for 4 h. The hydrogenation catalyst D4 was obtained by impregnating the support by the equal volume impregnation method, drying at 100°C for 10 h, and calcining at 500°C for 3 h. The physicochemical properties of the obtained catalyst are listed in Table 2.

[0098] Comparative Example 5

[0099] An aluminum chloride solution with a concentration of 30 g Al2O3 / L and a water glass solution with a concentration of 30 g SiO2 / L and a modulus of 2.5 were prepared and kept ready for use. A sodium metaaluminate solution with a caustic ratio of 1.20 and a concentration of 100 g Al2O3 / L was prepared and kept ready for use. A sol was prepared by stirring and mixing 60 g of methyl orthosilicate, 80 g of tetrapropylammonium hydroxide (TPAOH), and 40 g of deionized water, and then the mixture was stirred and aged at 80°C for 8 h to obtain a precursor solution.

[0100] Into a 5000 mL reactor, 700 mL of deionized water was added as a bottom water, the stirring was started and heated, after the deionized water was heated to 70°C, the prepared aluminum chloride solution was added to the reactor at a rate of 14 mL / min, while the prepared sodium metaaluminate and water glass were added in parallel flow, the pH of the reaction was controlled to be 6.0 by adjusting the flow rate of sodium metaaluminate and water glass, and the temperature and pH of the slurry in the reactor were kept constant. After the reaction was completed, the amount of aluminum chloride was 1100 ml, the amount of sodium metaaluminate was 500 mL, and the amount of water glass was 950 ml, then 45 g of precursor solution was added to the above solution and stirred until mixed uniformly.

[0101] The above slurry was placed in a reactor, and under stirring, the treatment temperature was 120°C, the treatment pressure was 0.2 MPa, and the treatment time was 4 h. The treated slurry was washed with hot water at 70°C until the liquid was neutral, and then dried at 120°C for 8 h to obtain the carrier precursor B-2.

[0102] (2) Catalyst preparation

[0103] Molybdenum oxide (content 99%) 38.86 g, basic nickel carbonate (nickel oxide content 54 wt%) 17.81 g, and phosphoric acid 17.88 g were weighed and heated to prepare an impregnation solution of 500 ml. Carrier precursor B-2 400 g (dry basis 70 wt%) and hydroxymethyl cellulose 11.2 g were mixed, 100 ml of the above impregnation solution was taken and diluted ten times, then added to the above mixture and kneaded, extruded into strips, dried at 100°C for 6 h, and calcined at 600°C for 6 h to obtain a hydrogenation catalyst carrier; the carrier was impregnated by the equal volume impregnation method, dried at 110°C for 8 h, and calcined at 600°C for 3 h to obtain a hydrogenation catalyst D5. The physicochemical properties of the obtained catalyst are listed in Table 2.

[0104] Comparative Example 6

[0105] An aluminum nitrate solution with a concentration of 70 g Al203 / L and a silica sol solution with a concentration of 80 g Si02 / L and a modulus of 2.8 were prepared and kept ready for use. A potassium meta-aluminate solution with a caustic ratio of 1.20 and a concentration of 170 g Al203 / L was prepared and kept ready for use. 30 g of the silica sol, 20 g of deionized water were stirred to form a sol, and then 15 g of ethylene glycol was mixed therewith to age at 80°C for 8 h to obtain a precursor solution. 1000 mL of deionized water was added to a 5000 mL reactor as a bottom water, and stirring was started and heating was started. After the deionized water was heated to 70°C, the prepared aluminum nitrate solution was added to the reactor at a rate of 18 mL / min, and the prepared potassium meta-aluminate and silica sol were added in a concurrent flow. The pH of the reaction was controlled to be 6.0 by adjusting the flow rates of the potassium meta-aluminate and the silica sol, and the temperature and pH of the slurry in the reactor were kept constant. After the reaction was completed, the amount of aluminum nitrate was 1500 mL, the amount of potassium meta-aluminate was 700 mL, and the amount of silica sol was 1300 mL, and then 50 g of the precursor solution was added to the above solution and stirred until it was uniformly mixed. The above slurry was placed in the reactor, and under the condition of stirring, the treatment temperature was 180°C, the treatment pressure was 0.5 MPa, and the treatment time was 0.5 h. The treated slurry was washed with hot water at 80°C until the liquid was neutral, and then dried at 100°C for 10 h to obtain the support precursor B-3.

[0106] (2) Catalyst preparation

[0107] Molybdenum oxide (content 99%) 186.98 g, basic nickel carbonate (nickel oxide content 54 wt%) 68.56 g, phosphoric acid 45.90 g were weighed and prepared into 500 ml of impregnation solution by heating. The support precursor B-3 400 g (dry basis 70 wt%) and hydroxypropyl methyl cellulose 5.6 g were mixed, 100 ml of the above impregnation solution was taken and diluted ten times, and then added to the above mixture and kneaded, and then extruded into a strip, dried at 110°C for 6 h, and calcined at 500°C for 5 h to obtain a hydrogenation catalyst support. The support was impregnated by the equal volume impregnation method, dried at 90°C for 10 h, and calcined at 400°C for 4 h to obtain a hydrogenation catalyst D6. The physicochemical properties of the obtained catalyst are listed in Table 2.

[0108] Table 1 Catalysts of the examples

[0109] No. A B C Specific surface area, m 2 / g]] 191 225 182 Pore volume, mL / g 0.63 0.67 0.51 Pore size distribution > 100 nm 18 15 11 8-20 nm 60 51 46 Catalyst composition, wt% MoO3 7.32 5.92 22.02 NiO 2.21 1.38 4.51 P 0.82 0.71 1.52 Lateral pressure strength, N / mm 12.7 11.9 12.9 Metal dispersion IMo / IAl 0.068 0.06 0.151 INi / IAl 0.035 0.022 0.067 B acid, mmol / g 0.119 0.122 0.131

[0110] Table 2 Catalysts of the comparative examples

[0111]

[0112]

[0113] From the comparison of the data in Table 1 and Table 2, it can be seen that the hydrogenation catalyst prepared by the method of the present application has higher side pressure strength, better metal dispersion, and higher B acid content, and is more suitable for use as a heavy oil hydrogenation catalyst.

[0114] The above catalyst was subjected to activity evaluation on a continuous stirring autoclave (CSTR), and the catalyst was loaded at 100 mL. The ebullated bed reactor is similar to the continuous stirred tank reactor (CSTR), and both have good full back mixing performance and equivalent reaction kinetics characteristics. Therefore, the CSTR can be used to replace the ebullated bed reactor to evaluate the catalyst performance. The properties of the raw oil for evaluation are shown in Table 3. The evaluation conditions are as follows: reaction temperature 420℃, reaction pressure 15 MPa, hydrogen / oil volume ratio 500:1, volume space velocity 0.4h-1, and hydrogenation product yield 99.5% or above. -1 The data of Comparative Example 1 is taken as 100 as a benchmark, and the evaluation results of the other examples after activity comparison with Comparative Example 1 are shown in Table 4, and the values are taken by using the rounding method.

[0115] Table 3 Properties of raw oil

[0116]

[0117]

[0118] Table 4 Catalyst evaluation results

[0119]

Claims

1. A method for preparing a heavy oil hydrotreating catalyst, the method comprising the following steps: S1: Preparation of the carrier precursor; The method for preparing the carrier precursor includes the following steps: (1) Preparation of sol: Silicon source A, template agent and water are mixed evenly to obtain sol; the template agent is tetrapropylammonium hydroxide and / or tetrapropylammonium bromide; (2) After the sol obtained in step (1) is mixed evenly with alcohol, it is subjected to heat treatment to obtain material flow A. The heat treatment operation conditions are as follows: the treatment temperature is 60-100℃ and the treatment time is no more than 24 hours. (3) Add silicon source B, acidic aluminum source and alkaline aluminum source to a reactor containing bottom water. After the reaction, material stream B is obtained. Then, it is mixed evenly with nonionic surfactant to obtain material stream C. Then, material stream A is added to material stream C and stirred until it is evenly mixed to obtain slurry. The nonionic surfactant is one or more of polyethylene glycol, alkylolamide and polyether. (4) The slurry in step (3) is subjected to hydrothermal treatment under hydrothermal conditions, and then washed and dried to obtain the carrier precursor; S2: The carrier precursor obtained in step S1 is mixed with the additive, and then a solution containing active metal is added and kneaded. After the mixture is dried and calcined for the first time, the catalyst precursor is obtained. The auxiliary agent is one or more of methylcellulose, hydroxymethylcellulose, and hydroxypropyl methylcellulose, and the content of the auxiliary agent is 0.5-5 wt% based on the mass of the carrier precursor; S3: After introducing an active metal component onto the catalyst precursor obtained in step S2, the catalyst is dried and calcined a second time to obtain a heavy oil hydrogenation catalyst.

2. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, characterized in that: In step (1), silicon source A is one or more of tetraethyl orthosilicate, methyl orthosilicate, and silica sol.

3. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, characterized in that: In step (1), silicon source A is tetraethyl orthosilicate.

4. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: The template agent in step (1) is tetrapropylammonium hydroxide.

5. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: The alcohol in step (2) is a C1-C3 alcohol, which is one or more of monohydric alcohols, dihydric alcohols, and trihydric alcohols.

6. The method for preparing the heavy oil hydrotreating catalyst according to claim 1 or 5, characterized in that: The alcohol in step (2) is one or more of ethanol, ethylene glycol, and glycerol.

7. The method for preparing the heavy oil hydrogenation catalyst according to claim 6, characterized in that: The alcohol in step (2) is glycerol.

8. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, characterized in that: The weight ratio of silicon source A, template agent, water and alcohol is (3-6):(5-8):(2-4):(0.5-5).

9. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: The heat treatment conditions in step (2) are as follows: the treatment temperature is 80-100℃ and the treatment time is 8-12 hours.

10. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, characterized in that: In step (3), the silicon source B is water glass and / or alkaline silica sol.

11. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: In step (3), the silicon source B is an alkaline silica sol.

12. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: The acidic aluminum source in step (3) is a water-soluble acidic aluminum-containing compound.

13. The method for preparing the heavy oil hydrotreating catalyst according to claim 1 or 12, characterized in that: The acidic aluminum source in step (3) is a water-soluble acidic inorganic aluminum compound.

14. The method for preparing the heavy oil hydrotreating catalyst according to claim 1 or 12, characterized in that: The acidic aluminum source in step (3) is a water-soluble inorganic strong acid aluminum salt.

15. The method for preparing the heavy oil hydrogenation catalyst according to claim 1 or 12, characterized in that: The acidic aluminum source in step (3) is selected from one or more of aluminum sulfate, aluminum nitrate, and aluminum chloride.

16. The method for preparing the heavy oil hydrotreating catalyst according to claim 1 or 12, characterized in that: The acidic aluminum source in step (3) is aluminum sulfate.

17. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: The alkaline aluminum source in step (3) is an alkali metal aluminate solution, selected from one or more of sodium aluminate and potassium aluminate.

18. The method for preparing the heavy oil hydrotreating catalyst according to claim 1 or 17, characterized in that: The alkaline aluminum source in step (3) is sodium aluminate.

19. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: In step (3), the pH value of material flow B is 4 to 7; the pH value of material flow B is controlled by the amount of acidic aluminum source used.

20. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: In step (3), the pH value of material flow B is 5 to 6; the pH value of material flow B is controlled by the amount of acidic aluminum source used.

21. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: The reaction temperature in step (3) is 50℃~90℃.

22. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: The reaction temperature in step (3) is 50℃~80℃.

23. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, characterized in that: In step (3), the aluminum content of the acidic aluminum source is 10-70 gAl2O3 / L, the aluminum content of the alkaline aluminum source is 70-170 gAl2O3 / L, and the silicon content of silicon source B is 20-80 gSiO2 / L.

24. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: The nonionic surfactant in step (3) is polyethylene glycol, and the molecular weight of polyethylene glycol is 200 to 1000.

25. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, characterized in that: The alkylolamide is one or more of lauroyl diethanolamine and coconut oil fatty acid diethanolamide; the polyether is one or more of AEO-6 and AEO-9; and the molecular weight of the polyethylene glycol is 200 to 700.

26. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: The weight ratio of material flow A obtained in step (2) to material flow C in step (3) is 1:80~100.

27. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: The hydrothermal treatment conditions in step (4) are as follows: treatment temperature is 100℃~180℃; treatment pressure is 0.1~0.5MPa; treatment time is 0.5h~10h.

28. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, characterized in that: The hydrothermal treatment conditions in step (4) are as follows: the treatment temperature is 110℃~160℃; the treatment pressure is 0.1~0.3MPa; and the treatment time is 0.5h~6h.

29. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, characterized in that: The hydrothermal treatment conditions in step (4) are as follows: the treatment temperature is 120℃~150℃.

30. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: The drying conditions in step (4) are as follows: the drying temperature is 100-150℃ and the drying time is 6-10 hours.

31. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: The first drying conditions in step S2 are as follows: the first drying temperature is 90-120℃ and the first drying time is 2-10h; the first calcination conditions are as follows: the first calcination temperature is 500-800℃ and the first calcination time is 4-10h.

32. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: In step S2, the active metal is one or more of Group VIB metals and / or Group VIII metals. Based on the weight of the catalyst precursor and calculated as oxides, the concentration and amount of the solution containing the active metal are such that the content of Group VIII metals in the final catalyst precursor is 0.5-5 wt% and the content of Group VIB metals is 1.0-10.0 wt%.

33. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, characterized in that: In step S2, the active metal is one or more of Group VIB metals and / or Group VIII metals. Based on the weight of the catalyst precursor and calculated as oxides, the concentration and amount of the solution containing the active metal are such that the content of Group VIII metals in the final catalyst precursor is 1.0 to 3.0 wt% and the content of Group VIB metals is 2.0 to 5.0 wt%.

34. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, characterized in that: The active metal component mentioned in step S3 is one or more of Group VIB metals and / or Group VIII metals. Based on oxides and catalyst, the content of Group VIII metals in the final catalyst is 1.5 to 10.0 wt%, and the content of Group VIB metals is 5.0 to 25.0 wt%.

35. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, characterized in that: The active metal component mentioned in step S3 is one or more of Group VIB metals and / or Group VIII metals. Based on oxides and catalyst, the content of Group VIII metals in the final catalyst is 2.0 to 8.0 wt%, and the content of Group VIB metals is 10.0 to 20.0 wt%.

36. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, characterized in that: The second drying conditions in step S3 include: a second drying temperature of 90–120°C and a second drying time of 2–10 h; the second calcination conditions include: a second calcination temperature of 300–600°C and a second calcination time of 4–10 h.

37. A heavy oil hydrogenation catalyst, said catalyst being prepared by the method described in any one of claims 1-36.

38. The heavy oil hydrotreating catalyst according to claim 37, characterized in that: The hydrogenation catalyst includes a support and an active metal component. The support is made of silicon-aluminum material. The metal element in the active metal component comes from at least one of Group VIII metals and Group VIB metals. The Group VIII metal is one or two of Ni and Co, and the Group VIB metal is one or two of Mo and W.

39. The heavy oil hydrotreating catalyst according to claim 37, characterized in that: The heavy oil hydrotreating catalyst has the following properties: pore volume of 0.50-0.80 mL / g, and specific surface area of ​​150-280 m². 2 / g.

40. The heavy oil hydrotreating catalyst according to claim 37, characterized in that: The pore distribution of heavy oil hydrotreating catalysts has the following characteristics: pores with a diameter of 8-20 nm account for 40%-70% of the total pore volume, and pores with a diameter >100 nm account for more than 10% of the total pore volume.

41. The heavy oil hydrotreating catalyst according to claim 37, characterized in that: The diameter of the heavy oil hydrotreating catalyst is less than 1.5 mm, and the side pressure strength is greater than 10 N / mm.

42. The use of the heavy oil hydrogenation catalyst according to any one of claims 37-41 in the heavy oil hydrogenation reaction.

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