A catalyst carrier for hydrodemetallization, a catalyst and a method for preparing the same

Abstract

The application discloses a catalyst carrier for hydrodemetallization, a catalyst and a preparation method thereof. The preparation method of the catalyst carrier comprises the following steps: sealing and heat-treating alumina A after immersing the alumina A in an aqueous ammonium bicarbonate solution, and then drying to obtain a carrier component B; immersing an active carbon in the carrier component B to obtain a dispersion medium containing an active metal component, and then mixing and kneading the dispersion medium with the carrier component B to form a carrier C, and then roasting the carrier C to obtain the carrier C; sealing and treating the carrier C after immersing the carrier C in an aqueous ammonium bicarbonate solution, and then drying to obtain a carrier. When the catalyst prepared by using the carrier is used for a residual oil hydrodemetallization reaction, the activity and stability of the reaction can be obviously improved.

Description

Technical Field

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

[0002] With the increasing trend of heavier and lower-quality crude oil worldwide, the efficient processing and utilization of heavy and residual oils has become crucial. Most residual oil hydrotreating catalysts are supported catalysts, with the active metal components typically loaded onto the surface of a support. Under the action of the catalyst, various metal compounds react with H₂S to form metal sulfides, which are then deposited on the catalyst and removed. Therefore, the pore properties of the catalyst not only affect the distribution of active metals on the catalyst surface but also influence the deposition of other impurities after the reaction.

[0003] CN105983417A discloses a method for preparing a hydrodemetallization catalyst for residual oil, comprising the following steps: mixing one or more of alumina trihydrate, boehmite, pseudoboehmite and amorphous aluminum hydroxide with a peptizing agent, an extrusion aid, and an organic solution, then molding, drying and calcining to obtain a support; impregnating the obtained support with a solution containing nickel and molybdenum and drying and calcining to obtain the final catalyst.

[0004] CN108745392A discloses a hydrogenation demetallization catalyst with a bimodal pore distribution and its preparation method. The hydrogenation active metal component contained in the catalyst is selected from at least one group VIB metal component and at least one group VIII metal component. The specific preparation method includes mixing an alumina precursor with an extrusion aid, adding a metal salt solution containing the hydrogenation active metal component, kneading, molding, and drying, followed by hydrothermal treatment, drying, and calcination.

[0005] Because heavy oil feedstocks contain a large number of macromolecules, residue hydrodemetallization catalysts should possess a well-ventilated pore structure. Furthermore, to ensure the active metal components fully exert their hydrotreating effect, the active metals should be well dispersed both inside and on the surface of the catalyst, preventing their accumulation in the external pores and orifices. Currently, in the field of residue hydrotreating catalysts, the impregnation method used in catalyst preparation is still primarily aqueous solution impregnation, which involves single-phase impregnation of the metal dispersed in an aqueous solution. Due to the influence of the impregnation process's spray angle and wetting conditions, the degree of dispersion of the active metal on the catalyst surface is limited. Therefore, the activity and stability of the alumina support and hydrodemetallization catalysts prepared by the above methods still need further improvement. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a catalyst support, a catalyst, and a method for preparing the same for hydrodemetallization. When the catalyst of this invention is used in the hydrodemetallization reaction of residue oil, it can significantly improve the activity and stability of the reaction.

[0007] The first aspect of this invention provides a method for preparing a catalyst support for hydrodemetallization, comprising the following steps:

[0008] (1) After immersing aluminum oxide A in a first ammonium bicarbonate aqueous solution, it is sealed and heat-treated, and then dried to obtain carrier component B; wherein, the preparation method of aluminum oxide A includes: mixing aluminum nitrate, urea, template agent and water to obtain mixed solution X, crystallizing, calcining to obtain aluminum oxide A;

[0009] (2) Impregnate activated carbon with impregnation solution B containing active metal components to obtain a dispersion medium containing active metal components;

[0010] (3) Mix the carrier component B and the dispersion medium obtained in step (2), shape them, and calcine them to obtain the carrier C;

[0011] (4) The carrier C obtained in step (3) is immersed in the second ammonium bicarbonate aqueous solution, sealed and dried to obtain the carrier.

[0012] In step (2) of the present invention, the impregnation solution B containing the active metal component is an aqueous solution of an active metal containing Group VIB metals, Group VIII metals and optional additives.

[0013] In step (2) of the present invention, the method for preparing impregnation solution B is preferably to first mix the co-emulsifier, the group VIB metal source, water, and optional auxiliary agent source, and heat them to obtain a clear solution; then add the group VIII metal source to the obtained clear solution to obtain an aqueous solution containing active metal, i.e., impregnation solution B.

[0014] In the preparation method of impregnation solution B in this invention, the co-emulsifier is selected from one or more of hexadecyl alcohol, octadecyl alcohol, propylene glycol, n-butanol, ethylene alcohol, and glycerol.

[0015] In the preparation method of impregnation solution B of the present invention, the amount of the co-emulsifier is 0.5% to 5.0% of the mass of the obtained aqueous solution containing active metal.

[0016] In the preparation method of impregnation solution B of the present invention, the Group VIB metal is Mo and / or W. The Group VIB metal source is one or more of ammonium molybdate, ammonium metatungstate, and molybdenum oxide. The Group VIII metal is Ni and / or Co. The Group VIII metal source is one or more of basic nickel carbonate, cobalt nitrate, etc. The auxiliary agent source is at least one of fluorine, phosphorus, silicon, or boron, preferably phosphorus; wherein, the phosphorus source may be one or more of phosphoric acid, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate; the fluorine source is ammonium fluoride; the silicon source is silica sol; and the boron source is boric acid.

[0017] In the preparation method of impregnation solution B of the present invention, the water is distilled water or deionized water, and the conductivity of the water should be less than 10.0 mS.

[0018] In the preparation method of impregnation solution B of the present invention, the heating is carried out at a temperature of 90-120°C to ensure that the added substances are mixed evenly to form a clear solution.

[0019] In the preparation method of the impregnation solution B of the present invention, the concentration of Group VIB metals as oxides in the impregnation solution B is 8-70 g / 100 mL, preferably 8-60 g / 100 mL, the concentration of Group VIII metals as oxides is 2-50 g / 100 mL, preferably 5-40 g / 100 mL, and the mass concentration of additives as oxides is 0-18.0 g / 100 mL, preferably 0.2-16.0 g / 100 mL.

[0020] In step (1) of this invention, during the preparation of aluminum oxide A, aluminum nitrate, urea and template agent are dissolved in water (preferably deionized water) in the order of dissolving and mixing to obtain solution X.

[0021] In step (1) of the present invention, the molar ratio of Al(NO3)3 to the template agent is 160 to 240, preferably 180 to 220.

[0022] In step (1) of this invention, the molar ratio of urea to Al(NO3)3 is 7–14. Within this range, the OH- produced by the decomposition of urea... - Quantity and Al 3+ The hydrolysis rate is well-matched, and the generated alumina can grow uniformly on the template agent surface.

[0023] In step (1) of the present invention, the template agent is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methylcellulose, preferably polyethylene glycol; the viscosity of the template agent (20°C) is 10 to 1000 mPa·s, and the viscosity of solution X (20°C) after adding the template agent and stirring evenly is 120 to 660 mPa·s.

[0024] In step (1) of the present invention, the crystallization temperature is 80-200℃ and the crystallization time is 25-35h.

[0025] In step (1) of this invention, the crystallization process is carried out in a crystallization kettle.

[0026] In step (1) of this invention, after crystallization, the product can be filtered and washed using conventional and known methods, followed by drying, calcination, and alumina A. Washing can be performed with deionized water until the pH of the filtrate is close to neutral.

[0027] In step (1) of this invention, the drying temperature is 120-200℃ and the drying time is 2-12h.

[0028] In step (1) of this invention, the calcination temperature is 500-750℃, the calcination time is 2-6h, and the calcination atmosphere is air.

[0029] In step (1) of this invention, the mass percentage concentration of the first ammonium bicarbonate aqueous solution ranges from 10% to 20%. The sealing heat treatment temperature is 80 to 140°C, preferably 90 to 140°C, and the treatment time is 6 to 12 hours. The drying temperature is 120 to 180°C, and the drying time is 2 to 10 hours.

[0030] In step (2) of the present invention, the amount of MoO3 introduced into the catalyst by the impregnation solution B is 45% to 70% of the total MoO3 loading in the catalyst, and the amount of Group VIII metal oxides introduced into the catalyst by the impregnation solution B is 45% to 70% of the total Group VIII metal oxide loading in the catalyst.

[0031] In step (2) of this invention, saturated impregnation is used. After impregnation, the mixture is allowed to stand and then dried to obtain a dispersion medium containing the first active metal component.

[0032] In step (2) of this invention, the settling time is 4 to 12 hours.

[0033] In step (2) of this invention, the drying temperature is 20-200℃ and the drying time is 2-12h.

[0034] In step (3) of the present invention, the mass ratio of activated carbon to carrier component B in the dispersion medium obtained in step (2) is 0.10 to 0.50, for example, 0.10, 0.12, 0.14, 0.16, 0.18, 0.20, 0.22, 0.24, 0.26, 0.28, 0.30, 0.32, 0.34, 0.36, 0.38, 0.40, 0.42, 0.44, 0.46, 0.48, 0.50, etc., and any value within the range formed by any two of these values.

[0035] In step (3) of the present invention, conventional molding aids, such as adhesives, extrusion aids, etc., can be added as needed during the molding process. The adhesive is one or more of nitric acid, sulfuric acid, and oxalic acid, preferably nitric acid; the extrusion aid is one or more of guar gum powder, cellulose, and resin, preferably guar gum powder.

[0036] In step (3) of the present invention, the mass percentage of the adhesive solvent added accounts for 0.5% to 4.0% of the mass of carrier component B, and the mass percentage of the extrusion aid added accounts for 0.1% to 5.0% of the mass of carrier component B.

[0037] In step (3) of this invention, after molding, the substrate is dried and calcined to obtain carrier C. The drying temperature is 20-200℃ and the drying time is 2-12h.

[0038] In step (3) of this invention, the calcination temperature is 500-750℃, the calcination time is 2-6h, and the calcination atmosphere is air.

[0039] In step (4) of this invention, the mass percentage concentration of the second ammonium bicarbonate aqueous solution ranges from 20% to 30%. The sealing treatment temperature is 10–60°C, preferably 20–50°C, and the treatment time is 6–12 hours. The treatment temperature in step (4) is 60–90°C lower than the heat treatment temperature in step (1). The drying temperature is 10–40°C, the drying time is 2–10 hours, and the drying method is static drying.

[0040] In step (4) of this invention, the mass concentration of the second ammonium bicarbonate aqueous solution is 8 to 15 percentage points higher than that of the first ammonium bicarbonate aqueous solution in step (1).

[0041] A second aspect of the present invention provides a method for preparing a catalyst for hydrodemetallization, comprising the following steps:

[0042] (I) Preparing the impregnation solution, the steps of which include:

[0043] A water-soluble polymer is added to an aqueous solution containing a group VIB metal, a group VIII metal, and an optional additive, i.e., an active metal, to obtain an aqueous phase. The aqueous phase is then added dropwise to an oil phase to obtain an impregnation solution C.

[0044] (II) The carrier obtained by the above method (referred to as carrier D in this invention) is impregnated with impregnation solution C, allowed to stand, a surfactant is added, and the carrier is subjected to ultrasonic treatment and calcination to obtain the catalyst.

[0045] In step (I) of the present invention, the impregnation solution A is an aqueous solution of an active metal containing Group VIB metals, Group VIII metals, and optional additives.

[0046] In step (I) of the present invention, the method for preparing impregnation solution A preferably involves first mixing a co-emulsifier, a Group VIB metal source, water, and an optional auxiliary agent source, heating the mixture to obtain a clear solution; then adding a Group VIII metal source to the obtained clear solution to obtain an aqueous solution containing an active metal, i.e., impregnation solution A.

[0047] In step (I) of the present invention, the co-emulsifier is selected from one or more of hexadecyl alcohol, octadecyl alcohol, propylene glycol, n-butanol, ethylene alcohol and glycerol.

[0048] In step (I) of the present invention, the amount of the co-emulsifier is 0.5% to 5.0% of the mass of the obtained aqueous solution containing active metal.

[0049] In step (I) of this invention, the Group VIB metal is Mo and / or W. The Group VIB metal source is one or more of ammonium molybdate, ammonium metatungstate, and molybdenum oxide. The Group VIII metal is Ni and / or Co. The Group VIII metal source is one or more of basic nickel carbonate, cobalt nitrate, etc. The auxiliary agent source is at least one of fluorine, phosphorus, silicon, or boron, preferably phosphorus; wherein, the phosphorus source may be one or more of phosphoric acid, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate; the fluorine source is ammonium fluoride; the silicon source is silica sol; and the boron source is boric acid.

[0050] In step (I) of this invention, the water is distilled water or deionized water, and the conductivity of the water should be less than 10.0 mS.

[0051] In step (I) of the present invention, the heating is carried out to a temperature of 90-120°C to ensure that the added substances are mixed evenly to form a clear solution.

[0052] In step (I) of the present invention, the concentration of Group VIB metals as oxides in the impregnation solution A is 8-70 g / 100 mL, preferably 8-60 g / 100 mL, the concentration of Group VIII metals as oxides is 2-50 g / 100 mL, preferably 5-40 g / 100 mL, and the mass concentration of the additives as oxides is 0-18.0 g / 100 mL, preferably 0.2-16.0 g / 100 mL.

[0053] In step (I) of this invention, the water-soluble polymer is one or more of polyvinyl alcohol (molecular weight 170,000 to 220,000), carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate (molecular weight less than 10,000).

[0054] In step (I) of this invention, the mass concentration of the water-soluble polymer in the aqueous phase is 4.0–14.0%.

[0055] In step (I) of the present invention, preferably, a surfactant is added to oil and heated to obtain an oil phase.

[0056] In step (I) of this invention, the surfactant is selected from glyceryl monostearate, glyceryl distearate, glyceryl monolaurate, and polyoxyethylene ether fatty alcohol (structure R-(OCC)). x -OH, where R is a straight-chain alkyl group with 12 to 15 carbon atoms, and x is 2 to 11, etc., or one or more of these. The oil may be at least one of silicone oil and vegetable oil, wherein the silicone oil is selected from at least one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen silicone oil, and methyl phenyl silicone oil, and the vegetable oil is selected from one or more of peanut oil, coconut oil, and tea seed oil.

[0057] In step (I) of the present invention, the heating is carried out at a temperature of 40-80°C so that the oil phase presents a uniform liquid state.

[0058] In step (I) of this invention, the mass ratio of the surfactant added to the oil is 1.0:0.1 to 10, preferably 1.0:2 to 10, for example 1.0:2.0, 1.0:2.5, 1.0:3.0, 1.0:3.5, 1.0:4.0, 1.0:4.5, 1.0:5.0, 1.0:5.5, 1.0:6.0, 1.0:6.5, 1.0:7.0, 1.0:7.5, 1.0:8.0, 1.0:8.5, 1.0:9.0, 1.0:9.5, 1.0:10.0, etc., and any value within any range formed by any two of these values.

[0059] In step (I) of the present invention, the oil phase is kept in a liquid state at a temperature of 45-85°C and the stirring rate is 400-800 r / min.

[0060] In step (I) of the present invention, the mass ratio of the aqueous phase to the oil phase is 0.4 to 1.8:1.0, preferably 0.5 to 1.5:1.0, for example 0.5:1.0, 0.7:1, 0.9:1.0, 1.0:1.0, 1.2:1.0, 1.3:1.0, 1.5:1.0, 2.0:1.0, 3.0:1.0, 4.0:1.0, 5.0:1.0, 6.0:1.0, 7.0:1.0, 8.0:1.0, 9.0:1.0, etc., and any value within the range formed by any two of these values.

[0061] In step (I) of this invention, stirring and shearing homogenization are performed during the dropwise addition of the aqueous phase to the oil phase. The stirring and shearing homogenization process involves a stirring speed of 10,000–18,000 rpm, a shearing homogenization time of 3–8 min, and a temperature of 50–85°C.

[0062] In step (I) of this invention, the particle size of the water-in-oil droplets in the impregnation solution C is 5-20 nm.

[0063] In this invention, preferably, impregnation solution A and impregnation solution B can be the same, and the preferred preparation methods for each impregnation solution include:

[0064] (I-1) Divide the aqueous solution containing Group VIB metals and Group VIII metals and optional additives into two portions, labeled as impregnation solution A and impregnation solution B, respectively.

[0065] (I-2) Add water-soluble polymer to the impregnation solution A obtained in step (I-1) to obtain an aqueous phase. Add the aqueous phase dropwise to the oil phase to obtain impregnation solution C.

[0066] In this invention, the volume ratio of impregnation liquid A to impregnation liquid B is 0.6 to 4.0, preferably 0.5 to 2.5, for example 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.1, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, etc., and any value within the range formed by any two of these values.

[0067] In step (II) of this invention, the impregnation is carried out by saturation impregnation, and the standing time after impregnation is 4 to 14 hours.

[0068] In step (II) of the present invention, the amount of MoO3 introduced into the catalyst by the impregnation liquid C is 30% to 55% of the total MoO3 loading in the catalyst, and the amount of Group VIII metal oxides introduced into the catalyst by the impregnation liquid C is 30% to 55% of the total Group VIII metal oxide loading in the catalyst.

[0069] In step (II) of this invention, the surfactant is a polyether-type nonionic surfactant, preferably one or more of fatty alcohol polyvinyl chloride ether, ester polyvinyl chloride ether, phenolic polyvinyl chloride ether, and fatty amine polyvinyl chloride ether.

[0070] In step (II) of the present invention, the amount of surfactant used is 2.5% to 7.5% of the mass of the impregnation solution C.

[0071] In step (II) of this invention, the ultrasonic treatment includes: an ultrasonic frequency of 15-35 kHz, a material temperature of 35-75°C during the treatment process, and a time of 15-60 min.

[0072] In step (II) of this invention, after ultrasonic treatment, the catalyst is dried and calcined to obtain the catalyst. The drying temperature is 120–200°C, and the drying time is 2–12 hours.

[0073] In step (II) of this invention, the calcination temperature is 350–500°C, the calcination time is 2–6 h, and the calcination atmosphere is a mixture of an inert atmosphere and other atmospheres, with a volume ratio of 0.5–3:1 between the inert atmosphere and other atmospheres. The inert atmosphere is primarily one or two of nitrogen and helium, while the other atmosphere is one or more of water vapor and air.

[0074] In step (II) of the present invention, the ratio of carbon content on the catalyst surface to alumina content in the support component is 0.16 to 0.60, preferably 0.20 to 0.50, and the ratio of activated carbon content to alumina content in the support component is 0.10 to 0.45.

[0075] A third aspect of the present invention provides a catalyst for hydrogenation demetallization prepared by the above-described preparation method, the catalyst comprising a support component, an active metal component, and carbon distributed on the catalyst surface, wherein the active metal component comprises molybdenum and a Group VIII metal, and the support component comprises alumina and activated carbon; wherein the ratio of the carbon content distributed on the catalyst surface to the alumina content in the support component is 0.16 to 0.60, preferably 0.20 to 0.50, and the ratio of the activated carbon content to the alumina content in the support component is 0.10 to 0.45.

[0076] In this invention, the active metal component includes molybdenum and a Group VIII metal, wherein the Group VIII metal is preferably nickel.

[0077] In this invention, based on the mass of the catalyst, the content of MoO3 is 10.0% to 25.0%, and the content of Group VIII metal oxides is 2.0% to 10.0%.

[0078] In this invention, the catalyst has a specific surface area of ​​170–200 m². 2 / g, with a pore volume of 0.65~1.00mL / g.

[0079] In this invention, preferably, the catalyst has a specific surface area of ​​175–195 m². 2 / g, with a pore volume of 0.65~0.85mL / g.

[0080] In this invention, the pore distribution of the catalyst is as follows: pores with a diameter of <30nm occupy 20% to 40% of the total pore volume, pores with a diameter of 30 to 100nm occupy 30% to 40% of the total pore volume, and pores with a diameter of 100nm to 300nm occupy 20% to 50% of the total pore volume.

[0081] In this invention, the strength of the catalyst is 10.0 to 20.0 N / mm.

[0082] In this invention, the catalyst further includes an auxiliary component, which is selected from at least one of fluorine, phosphorus, silicon, or boron, preferably phosphorus. Based on the mass of the catalyst, the content of the auxiliary component, calculated as oxides, is 0-6.0%, preferably 0.5%-6.0%.

[0083] Compared with the prior art, the present invention has the following beneficial effects:

[0084] Currently, the presence of numerous large molecules in heavy oil feedstocks places higher demands on the pore structure of hydrodemetallization catalysts and the degree of dispersion of active metals. Conventional supports and catalyst impregnation methods offer limited improvement in catalyst performance. Through extensive research, the inventors discovered that the alumina support prepared by the uniform precipitation method has a large specific surface area and a regular pore structure. After heat treatment with ammonium bicarbonate aqueous solution followed by sealing, its pore properties are adjusted, and the most probable pore size is significantly increased. To further improve the pore permeability of the support, a portion of the active metal aqueous impregnation solution B is impregnated on activated carbon. After standing and drying, an active metal dispersion medium is obtained. The obtained dispersion medium is then mixed with alumina, nitric acid, guar gum powder, and deionized water, kneaded, shaped, dried, and calcined to obtain a support with more unobstructed pores and a suitable specific surface area. Then, the shaped support is subjected to ammonium bicarbonate aqueous solution followed by sealing again to prevent the active metal components from accumulating around the pore openings during impregnation. Finally, a loaded "water-in-oil" impregnation solution C is impregnated by saturation, allowed to stand, and a polyether-type nonionic surfactant is added. After ultrasonic treatment and calcination, the catalyst of this invention is obtained.

[0085] This invention utilizes surfactants to effectively disperse a prepared aqueous phase containing active metals in an oil phase, forming an impregnation solution where the active metals are carried by the aqueous phase and dispersed within the oil phase matrix, namely, a "water-in-oil" type impregnation solution C. Using this impregnation solution to impregnate a catalyst support allows for the preparation of catalysts with a more uniform distribution of active metals both inside and on the surface of the support. The aqueous phase of impregnation solution C contains water-soluble polymers, which act as a "protective layer" for the colloidal particles, adsorbing onto the particle surface to form a "surface layer" of a certain thickness. This controls the particle size and maintains the particle size distribution, effectively preventing collisions and aggregation between particles. By introducing a polyether-type nonionic surfactant, the "surface layer" on the surface of the particles can be removed. Combined with ultrasonic treatment, the aqueous phase can be separated from the oil-based dispersion matrix and uniformly adsorbed into the internal pores and surface of the support. After calcination in a mixed atmosphere containing inert gas, the water-soluble polymers in the aqueous phase can not only form dotted carbon dots, but also appropriately adjust the acidity of the catalyst, weaken the interaction between the active metal and the support, and promote the dispersion of the active metal, thus obtaining a hydrogenation catalyst with a more uniform dispersion of the active metal.

[0086] This invention combines single-phase aqueous impregnation and two-phase water-in-oil impregnation to load active metals in two steps. In the single-phase aqueous impregnation, the first active metal component is further dispersed in activated carbon, a dispersion medium, and introduced during carrier molding, thus reducing the interaction between the metal and the alumina carrier. In the two-phase water-in-oil impregnation, the highly dispersed nature of the aqueous phase in the oil phase is utilized. The aqueous phase serves as the carrier matrix for the second active metal component, while the oil phase uniformly disperses the metal from the aqueous phase on the carrier surface and within the pores, penetrating deep into the pores and surface of the carrier.

[0087] Through comprehensive coordination of each step, the resulting catalyst not only has large pore volume and pore size, but also high mechanical strength and suitable specific surface area. When used in the hydrodemetallization reaction of residue oil, this catalyst can significantly improve the activity and stability of the hydrodemetallization reaction. Detailed Implementation

[0088] In this invention, the pore structure (SVD) and specific surface area of ​​the catalyst are characterized using the Mack ASAP-2420 physical adsorption instrument.

[0089] In this invention, the ZQJ-III intelligent particle strength tester is used to test the crushability of catalyst particles.

[0090] In this invention, the carbon / alumina mass ratio on the catalyst surface was determined using a NETZSCH STA409PC-QMS403C thermogravimetric-mass spectrometer (TG-MS).

[0091] The technical solutions and effects of the present invention will be further illustrated below with reference to the embodiments, but the invention is not limited to the following embodiments.

[0092] Example 11

[0093] In this example, the surfactant is glyceryl monostearate, the silicone oil is methyl silicone oil, and the mass ratio of surfactant to silicone oil is 3.2:8. The co-emulsifier is polyethylene glycol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, and the water-soluble polymer is polyvinyl alcohol. The mass ratio of co-emulsifier:molybdenum source (calculated as molybdenum oxide):phosphorus source (calculated as phosphorus oxide):nickel source (calculated as nickel oxide):water-soluble polymer:water is 20:271.4:48.7:82.2:35.2:400. The mass ratio of the aqueous phase to the oil phase is 0.7.

[0094] (0) Prepare the impregnation solution, as follows:

[0095] (0-1) Add the surfactant glyceryl monostearate to the silicone oil, heat to 75°C, and wait for the silicone oil to melt to obtain the oil phase;

[0096] (0-2) Add the co-emulsifier polyethylene glycol, molybdenum oxide and phosphoric acid to deionized water in sequence. Use a reflux condenser during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 500 r / min. When heated to 110°C, maintain this temperature for 6 hours. Maintain a constant stirring speed until a transparent and clear solution is obtained.

[0097] (0-3) Add basic nickel carbonate to the clear solution obtained in step (0-2) to obtain an active metal impregnation solution (MoO3 concentration is 49.35 g / 100 mL, NiO concentration is 12.14 g / 100 mL, P2O5 concentration is 10.18 g / 100 mL), and divide it into impregnation solution A and impregnation solution B at a volume ratio of 7:3;

[0098] (0-4) Add water-soluble polymer polyvinyl alcohol to the impregnation solution A obtained in step (0-3) to obtain an aqueous phase;

[0099] (0-5) The aqueous phase from step (0-4) is added dropwise to the oil phase obtained in step (0-1) in the form of droplets. During the dropwise addition, the temperature of the oil phase is maintained at 75°C, and the mixture is stirred. The shear homogenization rate is 12000 rpm, the shear homogenization time is 7 min, and the temperature during the shear homogenization process is 65°C. After the droplets are dispersed into an emulsion, a water-in-oil impregnation solution C is obtained.

[0100] (1) Weigh out appropriate amounts of aluminum nitrate, urea and template agent polyethylene glycol (viscosity 500 mPa·s), wherein the molar ratio of Al(NO3)3 to polyethylene glycol is 185 and the molar ratio of urea to Al(NO3)3 is 10. Dissolve the above substances in a certain amount of deionized water in the order of aluminum nitrate, urea and polyethylene glycol. After stirring magnetically for 5 hours to mix evenly, solution X (viscosity 340 mPa·s) is obtained.

[0101] (2) The obtained solution X was transferred to a crystallization vessel, and then the crystallization vessel was placed in an oven at 170°C. After reacting for 30 hours, the crystallization vessel was removed and cooled. A mixed slurry containing a white precipitate was obtained in the reaction vessel. The obtained white precipitate was filtered and washed several times until the pH value of the filtrate was close to 7. The white precipitate was placed in an oven to dry at 120°C for 6 hours. Then it was calcined in a muffle furnace at 600°C for 4 hours to obtain alumina A.

[0102] (3) The obtained alumina A is immersed in ammonium bicarbonate aqueous solution and then sealed and heat treated to obtain carrier component B. The mass percentage concentration of ammonium bicarbonate aqueous solution is 18%, the sealing heat treatment temperature is 90℃, the treatment time is 6h, the drying temperature is 140℃, and the drying time is 4h.

[0103] (4) Activated carbon is impregnated with impregnation solution B in a saturated impregnation manner. After impregnation, it is left to stand at room temperature (25℃) for 4 hours and then dried at 120℃ for 6 hours to form a dispersion medium containing some active metals.

[0104] (5) The carrier component B, nitric acid (68wt%), guar gum powder, dispersion medium, and deionized water are mixed, shaped, dried, and calcined to obtain carrier C; wherein, the mass content of nitric acid (68wt%) added is 2.5% of the mass content of carrier component B, the mass content of guar gum powder added is 1.5% of the mass content of carrier component B, the amount of activated carbon added in the dispersion medium is 20% of the mass of carrier component B, the amount of deionized water added is adjusted in real time according to the material state during the shaping process, the drying temperature is 120℃, the drying time is 6h, the calcination temperature is 750℃, and the calcination time is 4h (the heating rate is 2.5℃ / min);

[0105] (6) The obtained carrier C was immersed in an ammonium bicarbonate aqueous solution and then sealed and dried to obtain carrier D. The mass percentage concentration of the ammonium bicarbonate aqueous solution was 28%, the sealing temperature was 30℃, the treatment time was 6h, the drying temperature was 30℃, the drying time was 4h, and the drying method was static drying.

[0106] (7) The carrier D was impregnated with impregnation solution C using a saturated impregnation method. After impregnation, the sample was allowed to stand at room temperature (25℃) for 6 hours, and then fatty alcohol polyvinyl chloride ether (R = 12, x = 5) was added, with the amount being 3.5% of the mass of impregnation solution C. The sample was then ultrasonically treated for 30 minutes at a frequency of 25 kHz. During the treatment, the material temperature was 70℃, allowing the aqueous phase to separate from the oil phase, while the oil phase gradually accumulated. After phase separation, the sample was dried (at a temperature of 120℃ for 6 hours) and calcined at a temperature of 450℃ for 5 hours (heating rate of 2.0℃ / min) in a mixed atmosphere of nitrogen and air (nitrogen to air volume ratio of 2:1) to obtain the catalyst for hydrodemetallization of residue oil. The above-prepared hydrodemetallization catalyst for residue oil was named CAT-1. The physicochemical properties of the catalyst are shown in Table 1.

[0107] Example 2

[0108] Similar to Example 1, except that in this example, the surfactant is glyceryl distearate, the silicone oil is ethyl silicone oil, the mass ratio of surfactant to silicone oil is 2.6:8, the co-emulsifier is cetyl alcohol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, the water-soluble polymer is carboxymethyl cellulose, and the mass ratio of co-emulsifier:molybdenum source (calculated as molybdenum oxide):phosphorus source (calculated as phosphorus oxide):nickel source (calculated as nickel oxide):water-soluble polymer:water is 24:271.4:48.7:82.2:90.3:400. The mass ratio of aqueous phase to oil phase is 0.6.

[0109] (0) Prepare the impregnation solution, as follows:

[0110] (0-1) Add the surfactant glyceryl distearate to the silicone oil, heat to 80°C, and wait for the silicone oil to melt to obtain the oil phase;

[0111] (0-2) Add the co-emulsifier cetyl alcohol, molybdenum oxide and phosphoric acid to deionized water in sequence. Use a reflux condenser during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 600 r / min. When heated to 120°C, maintain this temperature for 4 hours. Maintain a constant stirring speed until a transparent and clear solution is obtained.

[0112] (0-3) Add basic nickel carbonate to the clear solution obtained in step (0-2) to obtain an active metal impregnation solution (MoO3 concentration is 49.35 g / 100 mL, NiO concentration is 12.14 g / 100 mL, P2O5 concentration is 10.18 g / 100 mL), and divide it into impregnation solution A and impregnation solution B at a volume ratio of 13:7;

[0113] (0-4) Add water-soluble polymer carboxymethyl cellulose to the impregnation solution A obtained in step (0-3) to obtain an aqueous phase;

[0114] (0-5) The aqueous phase from step (0-4) is added dropwise to the oil phase obtained in step (0-1) in the form of droplets. During the addition, the temperature of the oil phase is maintained at 70℃, and stirring is performed simultaneously. The shear homogenization rate is 13000 rpm, the shear homogenization time is 7 min, and the temperature during shear homogenization is 75℃. After the droplets are dispersed into an emulsion, a water-in-oil impregnation solution C is obtained. The residue oil hydrodemetallization catalyst CAT-2 is obtained. The properties of the obtained catalyst are shown in Table 1, and the experimental results of the catalyst are shown in Table 4.

[0115] Example 3

[0116] Similar to Example 1, except that in this example, the surfactant is glyceryl monolaurate, the silicone oil is phenyl silicone oil, the mass ratio of surfactant to silicone oil is 2:8, the co-emulsifier is propylene glycol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, and the water-soluble polymer is sodium polyacrylate. The mass ratio of co-emulsifier: molybdenum source (calculated as molybdenum oxide): phosphorus source (calculated as phosphorus oxide): nickel source (calculated as nickel oxide): water-soluble polymer: water is 28:271.4:48.7:82.2:111.3:400. The mass ratio of the aqueous phase to the oil phase is 0.8.

[0117] (0) Prepare the impregnation solution, as follows:

[0118] (0-1) Add the surfactant glyceryl monolaurate to the silicone oil, heat to 70°C, and wait for the silicone oil to melt to obtain the oil phase;

[0119] (0-2) Add the co-emulsifier propylene glycol, molybdenum oxide and phosphoric acid to deionized water in sequence. Use a reflux condenser during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 700 r / min. When heated to 120°C, maintain this temperature for 4 hours. Maintain a constant stirring speed until a transparent and clear solution is obtained.

[0120] (0-3) Add basic nickel carbonate to the clear solution obtained in step (0-2) to obtain an active metal impregnation solution (MoO3 concentration is 49.35 g / 100 mL, NiO concentration is 12.14 g / 100 mL, P2O5 concentration is 10.18 g / 100 mL), and divide it into impregnation solution A and impregnation solution B at a volume ratio of 3:2;

[0121] (0-4) Add water-soluble polymer sodium polyacrylate to the impregnation solution A obtained in step (0-3) to obtain an aqueous phase;

[0122] (0-5) The aqueous phase from step (0-4) is added dropwise to the oil phase obtained in step (1). During the dropwise addition, the temperature of the oil phase is maintained at 55℃, and stirring is performed simultaneously. The shear homogenization rate is 14000 rpm, the shear homogenization time is 4 min, and the temperature during the shear homogenization process is 85℃. After the droplets are dispersed into an emulsion, a water-in-oil impregnation solution C is obtained. The residue oil hydrodemetallization catalyst CAT-3 is obtained. The properties of the obtained catalyst are shown in Table 1, and the experimental results of the catalyst are shown in Table 4.

[0123] Example 4

[0124] Similar to Example 1, except that in this example, the surfactant is polyoxyethylene ether fatty alcohol (R = 12, x = 5), the silicone oil is methylphenyl silicone oil, the mass ratio of surfactant to silicone oil is 1.6:8, the co-emulsifier is n-butanol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, the water-soluble polymer is gelatin, and the mass ratio of co-emulsifier: molybdenum source (calculated as molybdenum oxide): phosphorus source (calculated as phosphorus oxide): nickel source (calculated as nickel oxide): water-soluble polymer: water is 28:271.4:48.7:82.2:51.3:400. The mass ratio of the aqueous phase to the oil phase is 0.9.

[0125] (0) Prepare the impregnation solution, as follows:

[0126] (0-1) Add the surfactant polyoxyethylene ether fatty alcohol to the silicone oil, heat to 65°C, and wait for the silicone oil to melt to obtain the oil phase;

[0127] (0-2) Add the co-emulsifier n-butanol, molybdenum oxide and phosphoric acid to deionized water in sequence. Use a reflux condenser during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 400 r / min. When heated to 120°C, maintain this temperature for 4 h. Maintain a constant stirring speed until a transparent and clear solution is obtained.

[0128] (0-3) Add basic nickel carbonate to the clear solution obtained in step (2) to obtain an active metal impregnation solution (MoO3 concentration is 49.35g / 100mL, NiO concentration is 12.14g / 100mL, P2O5 concentration is 10.18g / 100mL), and divide it into impregnation solution A and impregnation solution B with a volume ratio of 11:9;

[0129] (0-4) Add water-soluble polymer gelatin to the impregnation solution A obtained in step (3) to obtain an aqueous phase;

[0130] (0-5) The aqueous phase from step (0-4) is added dropwise to the oil phase obtained in step (0-1) in the form of droplets. During the addition, the temperature of the oil phase is maintained at 65℃, and stirring is performed simultaneously. The shear homogenization rate is 15000 rpm, the shear homogenization time is 5 min, and the temperature during shear homogenization is 55℃. After the droplets are dispersed into an emulsion, a water-in-oil impregnation solution C is obtained. The residue oil hydrodemetallization catalyst CAT-4 is obtained. The properties of the obtained catalyst are shown in Table 1, and the experimental results of the catalyst are shown in Table 4.

[0131] Example 5

[0132] The difference between this example and Example 1 is that: in step (1), the molar ratio of Al(NO3)3 to polyethylene glycol is 220, and the molar ratio of urea to Al(NO3)3 is 12; in step (5), the amount of activated carbon added to the dispersion medium is 30% of the amount of carrier B. A catalyst CAT-5 for hydrodemetallization of residue oil was prepared. The physicochemical properties of the catalyst are shown in Table 1.

[0133] Example 6

[0134] The difference between this example and Example 1 is as follows: In step (3), the mass percentage concentration of the first ammonium bicarbonate aqueous solution is 15%, the sealing heat treatment temperature is 120℃, the treatment time is 6h, and the drying temperature is 140℃, the drying time is 6h; in step (6), the mass percentage concentration of the second ammonium bicarbonate aqueous solution is 25%, the sealing treatment temperature is 35℃, the treatment time is 6h, and the drying temperature is 30℃, the drying time is 8h. A catalyst CAT-6 for hydrodemetallization of residue oil was obtained. The physicochemical properties of the catalyst are shown in Table 1.

[0135] Example 7

[0136] The difference between this example and Example 1 is that in step (7), fatty alcohol polyvinyl chloride ether (R = 12, x = 5) was added at a concentration of 5.0% of the impregnation solution mass, followed by ultrasonic treatment for 40 min at a frequency of 30 kHz. The material temperature during the treatment was 65 °C. CAT-7, a catalyst for the hydrodemetallization of residual oil, was thus obtained. The physicochemical properties of the catalyst are shown in Table 1.

[0137] Comparative Example 1

[0138] Compared with Example 1, the difference is that in step (1), the molar ratio of Al(NO3)3 to polyethylene glycol is 265, and the molar ratio of urea to Al(NO3)3 is 7.0. The above substances are dissolved in a certain amount of deionized water in the order of aluminum nitrate, urea, and polyethylene glycol. After being magnetically stirred for 4 hours and mixed evenly, solution X is obtained; thus, dCAT-1, a catalyst for the hydrodemetallization of residue oil, is prepared. The physicochemical properties of this catalyst are shown in Table 1.

[0139] Comparative Example 2

[0140] Compared with Example 1, the difference is that in step (6), the mass percentage concentration of the second ammonium bicarbonate aqueous solution is 32%, the sealing treatment temperature is 75°C, the treatment time is 7h, the drying temperature is 140°C, and the drying time is 8h; thus, dCAT-2, a catalyst for hydrodemetallization of residue oil, is obtained. The physicochemical properties of this catalyst are shown in Table 1.

[0141] Comparative Example 3

[0142] Compared with Example 1, the difference is that in step (4), the activated carbon was not impregnated with impregnation solution B, but in step (7), the support D was directly impregnated with the Mo-Ni-P "water-in-oil" impregnation solution prepared according to the method of Example 1 in a saturated impregnation manner; thus, dCAT-3, a catalyst for hydrodemetallization of residue oil, was obtained. The physicochemical properties of the catalyst are shown in Table 1.

[0143] Comparative Example 4

[0144] Similar to Example 1, except that the mass ratio of surfactant to silicone oil in step (0-1) is 0.64:8. The final catalyst obtained is dCAT-4. The physicochemical properties of this catalyst are shown in Table 1.

[0145] Comparative Example 5

[0146] Similar to Example 1, except that no water-soluble polymer was added to the mixture in steps (0-4) (derived from steps (0-3)). The final catalyst obtained was dCAT-5. The physicochemical properties of this catalyst are shown in Table 1.

[0147] Comparative Example 6

[0148] Similar to Example 1, except that in this example, the surfactant is glyceryl monostearate, the silicone oil is methyl silicone oil, the mass ratio of surfactant to silicone oil is 3.2:8, the co-emulsifier is polyethylene glycol, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, the nickel source is basic nickel carbonate, and the water-soluble polymer is polyvinyl alcohol. The mass ratio of co-emulsifier: molybdenum source (calculated as molybdenum oxide): phosphorus source (calculated as phosphorus oxide): nickel source (calculated as nickel oxide): water-soluble polymer: water is 20:271.4:48.7:82.2:35.2:400. The mass ratio of the aqueous phase to the oil phase is 0.7.

[0149] The steps for preparing the impregnation solution in this example are as follows:

[0150] (1) Add molybdenum oxide and phosphoric acid to deionized water in sequence. A reflux condenser is used during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 500 r / min. When the temperature is heated to 110°C, the temperature is maintained for 6 hours. The stirring speed is kept constant until a clear solution is obtained.

[0151] (2) Add basic nickel carbonate to the clear solution obtained in step (1) to obtain an active metal impregnation solution, and divide it into impregnation solution A (aqueous phase) and impregnation solution B in a volume ratio of 7:3.

[0152] (3) The surfactant glyceryl monostearate, silicone oil, co-emulsifier polyethylene glycol, and polyvinyl alcohol were added to the aqueous phase while stirring. The shear homogenization rate was 12,000 rpm, the shear homogenization time was 7 min, and the temperature during the shear homogenization process was 65℃. After the droplets were dispersed into an emulsion, a water-in-oil impregnation solution C was obtained. The final catalyst was dCAT-6. The physicochemical properties of this catalyst are shown in Table 1.

[0153] Comparative Example 7

[0154] Similar to Example 1, except that the ultrasonic frequency in step (7) was 10 kHz, the material temperature was 30 °C, and the treatment time was 10 min. The final catalyst obtained was dCAT-7. The properties of the obtained catalyst are shown in Table 1.

[0155] Comparative Example 8

[0156] Similar to Example 1, except that no ultrasonic treatment was used in step (7). The final catalyst obtained was dCAT-8. The properties of the obtained catalyst are shown in Table 1.

[0157] Table 1 Physicochemical properties of residue hydrodemetallization catalysts

[0158] Table 1 (Continued) Physicochemical Properties of Residue Hydrodemetallization Catalysts

[0159]

[0160] Evaluation test

[0161] The activity and stability tests of the residue hydrodemetallization catalysts CAT-1-CAT-7 and dCAT-1-dCAT-8 were conducted in a 200 mL fixed-bed hydrotreating apparatus. All catalysts used were strip-shaped with a length of 2–3 mm. The reaction conditions were: reaction temperature 385 °C, hydrogen partial pressure 13.0 MPa, and liquid hourly space velocity 1.0 h⁻¹. 1 With a hydrogen-to-oil volume ratio of 750, the demetallization rates (Ni+V) of each catalyst after 1500 h of reaction are shown in Table 3. The properties of vacuum residue oil as feedstock are shown in Table 2.

[0162] Table 2 Properties of Crude Oil

[0163] <![CDATA[Density (20°C), g / cm 3 > 1.017 S,wt% 2.64 N,wt% 0.53 Ni,mg / g 64.3 V,mg / g 118.2 CCR,wt% 16.1

[0164] Table 3. Test results of residue hydrodemetallization catalysts for each example.

[0165]

[0166] Table 3 continues with the test results of various residue hydrodemetallization catalysts.

[0167]

[0168] As can be seen from Tables 1, 2 and 3, the hydrodemetallization catalyst prepared according to the method of the present invention has a smooth pore structure and a large specific surface area. It exhibits high reactivity and stability during the reaction process and can well meet the requirements of hydrodemetallization process of heavy oil, especially residue oil.

Claims

1. A method for preparing a catalyst support for hydrodemetallization, comprising the following steps: (1) Alumina A is immersed in a first ammonium bicarbonate aqueous solution, then sealed and heat-treated, and dried to obtain carrier component B; wherein, The preparation method of aluminum oxide A includes: mixing aluminum nitrate, urea, template agent and water to obtain a mixture X, crystallizing, calcining to obtain aluminum oxide A; (2) Impregnate activated carbon with impregnation solution B containing active metal components to obtain a dispersion medium containing active metal components; (3) Mix the carrier component B and the dispersion medium obtained in step (2), shape them, and calcine them to obtain the carrier C; (4) The carrier C obtained in step (3) is immersed in the second ammonium bicarbonate aqueous solution, sealed and dried to obtain the carrier; In step (1), in the preparation method of alumina A, the molar ratio of Al(NO3)3 to template agent is 160~240; the molar ratio of urea to Al(NO3)3 is 7~14. In step (4), the mass percentage concentration of the second ammonium bicarbonate aqueous solution ranges from 20% to 30%. In step (4), the sealing temperature is 10~60℃ and the drying temperature is 10~40℃.

2. The preparation method according to claim 1, characterized in that, The impregnation solution B containing the active metal component is an aqueous solution of an active metal containing Group VIB metals, Group VIII metals, and optional additives. In the impregnation solution B, the concentration of Group VIB metals as oxides is 8~70g / 100mL, the concentration of Group VIII metals as oxides is 2~50g / 100mL, and the mass concentration of the additives as oxides is 0~18.0g / 100mL.

3. The preparation method according to claim 2, characterized in that, In the impregnation solution B, the concentration of Group VIB metals as oxides is 8~60g / 100mL, the concentration of Group VIII metals as oxides is 5~40g / 100mL, and the mass concentration of additives as oxides is 0.2~16.0g / 100mL.

4. The preparation method according to claim 2 or 3, characterized in that, The Group VIB metal is Mo; the Group VIII metal is Ni and / or Co.

5. The preparation method according to claim 1, characterized in that: In step (1), the template agent is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methylcellulose; And / or, in step (1), the crystallization temperature is 80~200℃ and the crystallization time is 25~35h; And / or, in step (1), the calcination temperature is 500~750℃ and the calcination time is 2~6h.

6. The preparation method according to claim 5, characterized in that: In step (1), the template agent is polyethylene glycol.

7. The preparation method according to claim 1, characterized in that, In step (1), the mass percentage concentration of the first ammonium bicarbonate aqueous solution ranges from 10% to 20%. And / or, the mass percentage concentration of the second ammonium bicarbonate aqueous solution in step (4) is 8 to 15 percentage points higher than the mass percentage concentration of the first ammonium bicarbonate aqueous solution in step (1).

8. The preparation method according to claim 1, characterized in that, In step (1), the sealing heat treatment temperature is 80~140℃ and the treatment time is 6~12h; the drying temperature is 120~180℃ and the drying time is 2~10h. And / or, in step (4), the sealing treatment time is 6~12h; the drying time is 2~10h; And / or, the sealing treatment temperature in step (4) is 60~90°C lower than the sealing heat treatment temperature in step (1).

9. The preparation method according to claim 8, characterized in that, In step (1), the sealing heat treatment temperature is 90~140℃; in step (4), the sealing treatment temperature is 20~50℃.

10. The preparation method according to claim 1, characterized in that, In step (3), the mass ratio of activated carbon to carrier component B in the dispersion medium obtained in step (2) is 0.10~0.

50.

11. A method for preparing a catalyst for hydrodemetallization, comprising the following steps: (I) Preparing the impregnation solution, the steps of which include: A surfactant is added to oil and heated to obtain an oil phase. The mass ratio of the surfactant to the oil is 1.0:0.1~10. A water-soluble polymer is added to an aqueous solution containing a Group VIB metal, a Group VIII metal, and an optional additive, i.e., an active metal, to obtain an aqueous phase. The aqueous phase is then added dropwise to an oil phase to obtain an impregnation solution C. Impregnation solution A is prepared by the following method: first, a co-emulsifier, a Group VIB metal source, water, and an optional additive source are mixed and heated to obtain a clear solution; then, a Group VIII metal source is added to the obtained clear solution to obtain an aqueous solution containing the active metal. (II) Impregnate the carrier obtained by any one of the preparation methods according to claims 1-10 with impregnation solution C, let it stand, add surfactant, sonicate, and calcine to obtain the catalyst; In step (II), the ultrasonic treatment includes: an ultrasonic frequency of 15~35kHz, a material temperature of 35~75℃, and a time of 15~60min.

12. The preparation method according to claim 11, characterized in that, In step (I), the impregnation solution A contains a concentration of 8-70 g / 100 mL of Group VIB metals as oxides, a concentration of 2-50 g / 100 mL of Group VIII metals as oxides, and a mass concentration of 0-18.0 g / 100 mL of additives as oxides. The Group VIB metal is Mo; the Group VIII metal is Ni and / or Co.

13. The preparation method according to claim 12, characterized in that, In step (I), the impregnation solution A contains a concentration of 8-60 g / 100 mL of Group VIB metals as oxides, a concentration of 5-40 g / 100 mL of Group VIII metals as oxides, and a mass concentration of 0.2-16.0 g / 100 mL of additives as oxides.

14. The preparation method according to claim 12, characterized in that, The volume ratio of impregnation solution A to impregnation solution B is 0.6 to 4.

0.

15. The preparation method according to claim 14, characterized in that, The volume ratio of impregnation solution A to impregnation solution B is 0.5~2.

5.

16. The preparation method according to claim 11, characterized in that, In step (I), the water-soluble polymer is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide, carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate.

17. The preparation method according to claim 16, characterized in that, In step (I), the mass concentration of the water-soluble polymer in the aqueous phase is 4.0% to 14.0%.

18. The preparation method according to claim 11, characterized in that, In step (I), the mass ratio of the aqueous phase to the oil phase is 0.4~1.8:1.

0.

19. The preparation method according to claim 18, characterized in that, In step (I), the mass ratio of the aqueous phase to the oil phase is 0.5~1.5:1.

0.

20. The preparation method according to claim 11, characterized in that, In step (II), the surfactant is a polyether-type nonionic surfactant; And / or, in step (II), the calcination temperature is 350~500℃, the calcination time is 2~6h, and the calcination atmosphere is a mixture of an inert atmosphere and other atmospheres; wherein, the inert atmosphere is one or two of nitrogen and helium, and the other atmosphere is one or more of water vapor and air.

21. The preparation method according to claim 20, characterized in that, In step (II), the amount of surfactant used is 2.5% to 7.5% of the mass of the impregnation solution C.

22. A catalyst for hydrodemetallization prepared by the method according to any one of claims 11-21.

23. The catalyst according to claim 22, characterized in that, The catalyst comprises a support component, an active metal component, and carbon distributed on the catalyst surface. The active metal component includes molybdenum and Group VIII metals, and the support component includes alumina and activated carbon. The ratio of carbon content on the catalyst surface to alumina content in the support component is 0.16 to 0.60, and the ratio of activated carbon content to alumina content in the support component is 0.10 to 0.

45.

24. The catalyst according to claim 23, characterized in that, The ratio of carbon content on the catalyst surface to alumina content in the support component is 0.20~0.

50.

25. The catalyst according to claim 23, characterized in that, Based on the mass of the catalyst, the content of MoO3 is 10.0%~25.0%, and the content of Group VIII metal oxide is 2.0%~10.0%, wherein the Group VIII metal is nickel.

26. The catalyst according to claim 23, characterized in that, The catalyst includes an auxiliary component, which is selected from at least one of fluorine, phosphorus, silicon or boron.

27. The catalyst according to claim 26, characterized in that, The auxiliary agent component is phosphorus.

28. The catalyst according to claim 26, characterized in that, Based on the mass of the catalyst, the content of the auxiliary component, calculated as oxide, is 0~6.0%.

29. The catalyst according to claim 28, characterized in that, Based on the mass of the catalyst, the content of the auxiliary component, calculated as oxide, is 0.5% to 6.0%.

30. The catalyst according to claim 23, characterized in that, The catalyst has a specific surface area of ​​170~200m². 2 / g, with a pore volume of 0.65~1.00mL / g; And / or, the pore distribution of the catalyst is as follows: pores with a diameter <30 nm occupy 20%~40% of the total pore volume, pores with a diameter of 30~100 nm occupy 30%~40% of the total pore volume, and pores with a diameter of 100 nm~300 nm occupy 20%~50% of the total pore volume; And / or, the strength of the catalyst is 10.0~20.0 N / mm.

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