A hydrodemetallization catalyst and a method for preparing the same

Abstract

The application discloses a kind of hydrodemetallization catalyst and preparation method thereof.The preparation method of the catalyst of the application comprises: preparing aqueous solution containing group VIB metal and group VIII metal and optional active metal auxiliary as water phase impregnation liquid B and "water-in-oil" type impregnation liquid C;Impregnation liquid B impregnates activated carbon to obtain modified activated carbon;Pseudo-boehmite, modified activated carbon and adhesive are mixed, shaped, calcined to obtain carrier C;Carrier C is subjected to surface carbon coating treatment, calcined to obtain carrier D;Impregnation liquid C impregnates carrier D, adds polyether type non-ionic surfactant, is subjected to ultrasonic treatment, calcined to obtain catalyst.The catalyst is used in the process of residual oil hydrodemetallization, has higher hydrodemetallization activity and metal capacity, and can ensure long-period operation of device.

Description

Technical Field

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

[0002] In recent years, crude oil resources have become increasingly scarce, and the trend of crude oil becoming heavier and of lower quality has intensified. Hydrotreating technology, as an important route for the lightening of heavy oils, also faces new challenges and problems under the current circumstances. Residue hydrotreating technology is a crucial means of lightening heavy oils in the petroleum refining process, and its development hinges on the research and development of catalysts with good activity and stability. Hydrodemetallization catalysts, preceding hydrodesulfurization agents and hydrocarbon removal agents, play a vital role in removing various metallic impurities from the feedstock. Therefore, developing hydrodemetallization catalysts with suitable activity and good stability is particularly important.

[0003] CN1289640A discloses a method for preparing a supported hydrodemetallization catalyst. The method includes taking a macroporous δ- and / or θ-phase alumina support, placing it in a spray-impregnation boiler, preparing a Group VIB metal compound and / or Group VIII metal compound into an ammonia solution or aqueous solution, and uniformly spraying it onto the support in an atomized manner. The sprayed catalyst is then directly fed into a calcination furnace at a temperature of 300-450℃, and then gradually heated to 460-550℃, maintaining this temperature for 1-5 hours in the presence of air.

[0004] CN105709765A discloses a method for preparing a hydrodemetallization catalyst for residual oil, comprising the following steps: (1) mixing a pore-expanding agent, boehmite dry powder, extrusion aid, and adhesive solvent into a plastic body, extruding and drying; (2) spraying the unsaturated carrier after drying in step (1) with a mixed solution of phosphoric acid and ammonium oxalate, subjecting the impregnated carrier to sealed heating treatment, with the treatment pressure being the self-generated pressure under sealed conditions, the treatment temperature being 120-160℃, and the treatment time being 6-12 hours, and the treated carrier being dried and calcined to obtain an alumina carrier; (3) impregnating the alumina prepared in step (2) with active components, and after impregnation, drying and calcining to obtain an alumina carrier for the hydrodemetallization catalyst of residual oil.

[0005] The activity and stability of the hydrogenation demetallization catalysts prepared by the above method still need to be further improved. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a hydrodemetallization catalyst and its preparation method. This catalyst, used in the hydrodemetallization process of residue oil, exhibits high hydrodemetallization activity and metal-containing capacity, ensuring long-term operation of the equipment.

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

[0008] (0) Preparation of the impregnation solution:

[0009] (0-1) Prepare an aqueous solution of an active metal containing Group VIB metals and Group VIII metals and optional additives as impregnation solution B;

[0010] (0-2) Add a water-soluble polymer to an aqueous solution containing a group VIB metal, a group VIII metal, and an optional additive, i.e., impregnation A, to obtain an aqueous phase. Add the aqueous phase dropwise to the oil phase to obtain impregnation solution C.

[0011] (1) Activated carbon was impregnated with impregnation solution B to obtain modified activated carbon;

[0012] (2) Mix the pseudoboehmite, the modified activated carbon obtained in step (1), and the adhesive, shape them, and calcine them to obtain carrier C;

[0013] (3) The carrier C obtained in step (2) is subjected to surface carbon coating treatment and calcined to obtain carrier D;

[0014] (4) The carrier D obtained in step (3) is impregnated with impregnation solution C, a polyether-type nonionic surfactant is added, and the catalyst is obtained by ultrasonic treatment and calcination.

[0015] In this invention, the method for preparing the impregnation solution includes:

[0016] (0-1) Divide the aqueous solution containing Group VIB metals and Group VIII metals and optional additives into two portions, labeled as aqueous phase impregnation solution A and aqueous phase impregnation solution B, respectively.

[0017] (0-2) Add water-soluble polymer to the aqueous phase impregnation solution A obtained in step (0-1) to obtain an aqueous phase. Add the aqueous phase dropwise to the oil phase to obtain impregnation solution C.

[0018] In step (0-1) or step (0-2) of the present invention, preferably, the co-emulsifier, the Group VIB metal source, water, and optional auxiliary agent source are first mixed and heated to obtain a clear solution, and then the Group VIII metal source is added to the clear solution to obtain an aqueous solution containing the active metal, namely impregnation solution A or impregnation solution B.

[0019] In step (0-1) or step (0-2) 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.

[0020] In step (0-1) or step (0-2) of this invention, the amount of the co-emulsifier is 0.5% to 5.0% of the mass of the resulting aqueous solution containing active metal.

[0021] In step (0-1) or step (0-2) of this invention, the Group VIB metal is Mo and / or W, and the Group VIB metal source is one or more of ammonium molybdate, ammonium metatungstate, and molybdenum oxide. The auxiliary agent 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.

[0022] In step (0-1) or step (0-2) of this invention, the water is distilled water or deionized water, and the conductivity of the water should be less than 10.0 mS.

[0023] In step (0-1) or step (0-2) of the present invention, the heating is carried out to a temperature of 90-120°C to ensure that the substances added in step (0-1) or step (0-2) are mixed evenly to form a clear solution.

[0024] In step (0-1) or step (0-2) of this invention, 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.

[0025] In step (0-1) or step (0-2) of the present invention, the concentration of Group VIB metals as oxides in the aqueous solution containing active metals is 8-75 g / 100 mL, preferably 10-60 g / 100 mL, the concentration of Group VIII metals as oxides is 2-55 g / 100 mL, preferably 5-30 g / 100 mL, and the mass concentration of the auxiliaries as oxides is 0-18.0 g / 100 mL, preferably 0.20-17.0 g / 100 mL.

[0026] In this invention, the volume ratio of impregnation liquid A to impregnation liquid B is 0.2 to 3.0, preferably 0.3 to 1.8, for example 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, etc., and any value within the range formed by any two of these values.

[0027] In step (0-2) 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).

[0028] In step (0-2) of this invention, the mass concentration of the water-soluble polymer in the aqueous phase is 4.0-14.0%.

[0029] In step (0-2) of this invention, preferably, a surfactant is added to the oil and heated to obtain an oil phase. Further, 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.

[0030] In step (0-2) of this invention, the temperature is heated to 45-85°C to make the oil phase appear as a uniform liquid.

[0031] In step (0-2) of this invention, the mass ratio of the added surfactant 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.

[0032] In step (0-2) of this 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.

[0033] In step (0-2) of this 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, 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.

[0034] In step (0-2) of this invention, stirring and shearing homogenization are performed during the dropwise addition of the aqueous phase to the oil phase. During the stirring and shearing homogenization process, the stirring speed is 10000–18000 rpm, the shearing homogenization time is 3–8 min, and the temperature during the shearing homogenization process is 50–85℃.

[0035] In step (0-2) of this invention, the particle size of the water-in-oil droplets in the impregnation solution C is 5-20 nm.

[0036] In step (1) of this invention, the method for preparing modified activated carbon includes:

[0037] (1-1) Impregnate activated carbon with impregnation solution B containing dispersant, dry and calcine to obtain modified activated carbon precursor;

[0038] (1-2) The modified activated carbon precursor obtained in step (1-1) is mixed with an alkaline additive, ground and dried to obtain modified activated carbon.

[0039] In step (1-1) of this invention, the activated carbon is high-temperature activated carbon. The minimum heat resistance temperature of the high-temperature activated carbon is 750℃. The particle size of the activated carbon is 0.1~6.0μm.

[0040] In step (1-1), the dispersing agent is silica sol. The silica sol contains 20.0% to 50.0% silica by mass.

[0041] In step (1-1), the mass content of the dispersing agent in impregnation solution B, calculated as silica, is 0.5% to 5.0%.

[0042] In step (1-1) of this invention, the impregnation method is saturated impregnation.

[0043] In step (1-1) of this invention, the drying conditions are: a temperature of 120–180°C and a drying time of 4–8 hours. The calcination conditions are: a temperature of 550–750°C and a time of 3–8 hours, and the calcination atmosphere is one or more of air, water vapor, and nitrogen.

[0044] In step (1-1) of this invention, the active metal in the system composed of Group VIB metals, Group VIII metals, and optional additives in impregnation solution B is a co-active metal. It can interact with the support during the calcination process to weaken the acidity of the support, and it can also synergistically interact with the active metal in the system composed of Group VIB metals, Group VIII metals, and optional additives in impregnation solution C, which is beneficial to the hydrogenation reaction.

[0045] In steps (1-2) of this invention, the alkaline auxiliary is one or more of alkaline compounds such as sodium hydroxide, potassium hydroxide, and sodium carboxylate (e.g., sodium acetate, sodium formate).

[0046] In step (1-2) of the present invention, the mass ratio of the alkaline additive to the activated carbon used in step (1-1) is 0.01 to 0.10.

[0047] In steps (1-2) of this invention, the grinding can be performed using methods such as ball milling or sand milling. The ground material not only exhibits more uniform metal dispersion, but the alkaline additive also forms a "first protective film" on the surface of the dried material during the molding process in steps (1-2). The resulting ground sample has an average particle size of 2.0–8.0 μm.

[0048] In step (1-2) of this invention, the drying conditions are: temperature of 120-180℃ and drying time of 4-8h.

[0049] In step (1) of the present invention, the amount of Group VIB metal oxide introduced into the catalyst by the impregnation solution B is 35% to 60% of the total Group VIB metal oxide loading in the catalyst, and the amount of Group VIII metal oxide introduced into the catalyst by the impregnation solution B is 35% to 60% of the total Group VIII metal oxide loading in the catalyst.

[0050] In step (2) of this invention, the pseudoboehmite is obtained by conventional methods, such as the aluminum sulfate method, aluminum alkoxide method, sol-gel method, etc. The alumina content in the pseudoboehmite is 65.0% to 80.0% by mass.

[0051] In step (2) of the present invention, the adhesive can be an inorganic acid and / or an organic acid. The inorganic acid can be one or more of nitric acid, sulfuric acid, boric acid, and phosphoric acid, and the organic acid can be one or more of tartaric acid, citric acid, and oxalic acid.

[0052] In step (2) of this invention, the mass fraction of the adhesive is 0.5% to 5.0% of the total mass of boehmite (calculated as alumina) and modified activated carbon.

[0053] In step (2) of this invention, the forming method can be at least one of extrusion, sheeting, and ball forming. The formed shape can be clover-shaped, four-leaf clover-shaped, butterfly-shaped, cylindrical, spherical, or strip-shaped, etc.

[0054] In step (2) of this invention, molding aids, such as at least one of extrusion aids and deionized water, can be added during the molding process according to molding requirements. The extrusion aid can be one or more of methylcellulose, ethylcellulose, guar gum, and starch. The mass of the extrusion aid added is 0.5% to 8.0% of the total mass of boehmite (calculated as alumina) and modified activated carbon. The amount of deionized water used can be 80% to 120% of the total mass of boehmite (calculated as alumina) and modified activated carbon.

[0055] In step (2) of the present invention, the drying temperature is 120-200℃ and the drying time is 2-12h.

[0056] In step (2) of this invention, the calcination process employs programmed temperature increase at a rate of 1°C / min to 3°C / min. The calcination temperature is 550°C to 750°C, the calcination time is 2 to 8 hours, and the calcination atmosphere is one or more of air, nitrogen, or water vapor, preferably air.

[0057] In step (3) of this invention, the carbon coating treatment preferably uses a mixed solution of a carbon-containing precursor and water-soluble cellulose. In the mixed solution, the mass content of the carbon-containing precursor is 8.0%–16.0%, and the mass content of the water-soluble cellulose is 0.5%–3.5%.

[0058] In step (3) of this invention, the carbon-containing precursor is one or more of polyimide, polyfurfuryl alcohol, phenolic resin, etc.

[0059] In step (3) of the present invention, the water-soluble cellulose is one or more of hydroxymethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, etc.

[0060] In step (3) of the present invention, the ratio of the amount of the mixed solution (in mL) to the amount of carrier C (in g) is 0.8 to 1.5 mL / g.

[0061] In step (3) of this invention, after the surface carbon coating treatment is completed, the carrier D is obtained through conventional filtration, washing, drying, and calcination. The drying conditions are: drying temperature of 120-200℃ and drying time of 2.0-12.0h. The calcination conditions are: calcination temperature of 500-700℃ and calcination time of 2.0-8.0h, and the calcination atmosphere is an inert atmosphere, which is one or more of nitrogen and argon.

[0062] In step (4) of this invention, the saturated immersion method is used for impregnation, and the standing time after impregnation is 4 to 14 hours.

[0063] In step (4) of the present invention, the amount of Group VIB metal oxide introduced into the catalyst by the impregnation liquid C is 40% to 65% of the total Group VIB metal oxide loading in the catalyst, and the amount of Group VIII metal oxide introduced into the catalyst by the impregnation liquid C is 40% to 65% of the total Group VIII metal oxide loading in the catalyst.

[0064] In step (4) of this invention, the surfactant is a polyether-type nonionic surfactant, preferably a fatty alcohol polyoxyethylene ether (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).

[0065] In step (4) of the present invention, the amount of surfactant used is 2.5% to 7.5% of the mass of the impregnation solution C.

[0066] In step (4) of this invention, the ultrasonic treatment conditions are as follows: the ultrasonic frequency is 15-35 kHz, the material temperature is 35-75 ℃, and the time is 15-60 min.

[0067] In step (4) of this invention, after ultrasonic treatment, the catalyst is obtained by drying and calcination. The drying temperature is 120-200℃ and the drying time is 2-12h.

[0068] In step (4) of this invention, the roasting process employs a two-stage roasting process. The first stage roasting temperature is 350–450°C, the roasting time is 2–6 hours, and the roasting atmosphere is one or more of air, nitrogen, or water vapor, preferably air. The second stage roasting temperature is 450–750°C, the roasting time is 2–8 hours, and the roasting atmosphere is one or more of air, nitrogen, or water vapor, preferably nitrogen. The second stage roasting temperature is 150–250°C higher than the first stage roasting temperature.

[0069] The second aspect of the present invention provides a hydrogenation demetallization catalyst obtained by any of the preparation methods described in the first aspect.

[0070] In this invention, the catalyst includes a support and a second active metal. The support includes alumina, activated carbon and a first active metal, wherein the mass ratio of alumina to activated carbon is 4.0 to 12.0:1, preferably 6.0 to 9.0:1.

[0071] In this invention, the first active metal comprises at least one group VIB metal and at least one group VIII metal, wherein the group VIB metal is preferably molybdenum and the group VIII metal is preferably nickel. The second active metal comprises at least one group VIB metal and at least one group VIII metal, wherein the group VIB metal is preferably molybdenum and the group VIII metal is preferably nickel.

[0072] In this invention, based on the mass of the catalyst, the content of Group VIB metal oxides is 9.0% to 35.0%, and the content of Group VIII metal oxides is 5.0% to 16.0%.

[0073] In this invention, based on the total mass of Group VIII metal oxides in the catalyst, the content of Group VIII metal oxides in the first active component is 35% to 60%, and the content of Group VIII metal oxides in the second active component is 40% to 65%.

[0074] In this invention, based on the total mass of Group VIB metal oxides in the catalyst, the content of Group VIB metal oxides in the first active component is 35% to 60%, and the content of Group VIB metal oxides in the second active component is 40% to 65%.

[0075] In this invention, the catalyst has a specific surface area of ​​150–180 m². 2 / g, with a pore volume of 0.60–0.90 mL / g; preferably, the catalyst has a specific surface area of ​​160–175 m² / g. 2 / g, with a pore volume of 0.70~0.85mL / g.

[0076] 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 2.0% to 8.0%.

[0077] The third aspect of this invention provides the application of the above-mentioned catalyst in the hydrotreating of heavy oil and residual oil.

[0078] Compared with the prior art, the present invention has the following beneficial effects:

[0079] In the hydrodemetallization of residual oil catalysts, hydrogenation and cracking reactions occur on the surface during the reaction. Generally, when the acidity of the catalyst surface is too strong, the hydrogenation products will continue to crack on the catalyst surface, leading to condensation and coking, which affects the catalyst activity. Through extensive research, the inventors discovered that firstly, impregnating the activated carbon surface with a first active metal in the form of metal ions, and then shaping it with boehmite, can effectively reduce the interaction between the metal and the alumina support. Secondly, a second active metal is introduced onto the catalyst through saturated impregnation. The first impregnation can control the acidity of the catalyst surface by controlling the metal content, while the second impregnation can further control the hydrogenation activity of the catalyst surface. This invention introduces the active metal in two stages, effectively controlling the active sites on the catalyst surface. While improving the overall performance of the catalyst, it also helps to extend the operating cycle of the unit.

[0080] Furthermore, conventional active metal loading involves a single impregnation, resulting in the active metal mostly distributed on the catalyst surface. This metal aggregation leads to low metal sulfidation and limited hydrogenation capacity. This invention introduces active metal through a two-stage impregnation process. First, a first active metal is impregnated onto activated carbon. A dispersing agent is introduced during this process to prevent metal aggregation during calcination, ensuring a uniform distribution of the first active metal on the activated carbon. Second, during grinding, an alkaline agent introduced onto the activated carbon forms a protective film during kneading, reducing the interaction between the metal and alumina. Then, a carbon film is applied to the support containing the first active metal. This carbon film ensures that the second active metal does not contact the first active metal or the support during subsequent impregnation, allowing for uniform dispersion of the second active metal on the carbon film. Finally, under a mixed atmosphere calcination, air removes the carbon film, leaving the second active metal uniformly dispersed on the support. In addition, carbon coating is performed on the support C, and the moisture gradually evaporates through inert gas calcination. The latex particles are gradually squeezed to form a film with crosslinkable groups in the structure. The crosslinking forms a three-dimensional network film, which temporarily provides a loading site for the second active metal. After the catalyst is calcined, the film disappears, and the second active metal is uniformly dispersed on the support and cooperates with the first active metal, which is beneficial to improving the activity and stability of hydrogenation demetallization.

[0081] In the preparation of the impregnation solution, this invention prepares an impregnation solution in which the active metal is dispersed in a carrying matrix, namely a "water-in-oil" type impregnation solution. Then, the catalyst support is impregnated using this impregnation solution, resulting in a catalyst with a more uniform distribution of active metals inside and on the surface of the support. First, the main active metal is fully dispersed in the carrying matrix water in ionic form using a co-emulsifier. Then, the auxiliary metal is dissolved in the above solution to obtain an aqueous phase containing both the main metal and the auxiliary metal. To control the particle size and maintain the particle size distribution during the subsequent formation of the "water-in-oil" emulsion, a water-soluble polymer is added to the obtained aqueous phase as a "protector" for the particles. This water-soluble polymer adsorbs onto the surface of the particles during the subsequent "water-in-oil" emulsion formation, forming a "surface layer" of a certain thickness, which effectively hinders collisions and aggregation between particles, further improving the stability of the system. Then, under specific conditions, the above aqueous phase is dispersed in an oil phase to obtain a hydrogenation catalyst impregnation solution. In the second impregnation process of this invention, the property of the highly dispersed aqueous phase in the oil phase is utilized. The aqueous phase serves as the carrier matrix for the metal components, while the oil phase uniformly disperses the metal in the aqueous phase on the surface and pores of the carrier. In this invention, the "water-in-oil" droplets can penetrate deep into the pores and surface of the carrier. Furthermore, 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 detach from the oil-based dispersion matrix and be uniformly adsorbed into the internal pores and surface of the carrier. Finally, after drying and calcining, the resulting impregnated carrier yields a hydrogenation catalyst with a more uniform dispersion of active metals.

[0082] In summary, the method of the present invention, through the comprehensive coordination of each step, significantly improves the activity and stability of the final residue oil hydrodemetallization catalyst. Detailed Implementation

[0083] In this invention, the pore structure and specific surface area of ​​the catalyst are characterized using the Mack ASAP-2420 physical adsorption instrument.

[0084] 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.

[0085] Example 1

[0086] (0) Preparation of the impregnation solution:

[0087] 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 3.5:8. 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, and the water-soluble polymer is carboxymethyl cellulose. The mass ratio of co-emulsifier, molybdenum source (calculated as molybdenum oxide), phosphorus source (calculated as phosphorus oxide), nickel source (calculated as nickel oxide), and water-soluble polymer to water is 20:267.1:53.4:64.1:35.2:400. The mass ratio of the aqueous phase to the oil phase is 0.9.

[0088] (0-1) Add the co-emulsifier cetyl alcohol, molybdenum oxide, and phosphoric acid to deionized water in that order. Use a reflux condenser during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 500 r / min. When the temperature is raised to 120°C, maintain this temperature for 4 hours. Maintain a constant stirring speed until a clear solution is obtained. Add basic nickel carbonate to the obtained clear solution to obtain an active metal impregnation solution (MoO3 concentration is 48.78 g / 100 mL, NiO concentration is 11.71 g / 100 mL, and P2O5 concentration is 9.76 g / 100 mL). Divide the solution into impregnation solution A and impregnation solution B at a volume ratio of 1:1.

[0089] (0-2) Water-soluble polymer carboxymethyl cellulose is added to the impregnation solution A obtained in step (0-1) to obtain an aqueous phase. The aqueous phase is then added dropwise to the oil phase. During the dropwise addition, the temperature of the oil phase is maintained at 80°C, and stirring is performed simultaneously. The shear homogenization rate is 15000 rpm, the shear homogenization time is 5 min, and the temperature during the shear homogenization process is 60°C. After the droplets are dispersed into an emulsion, a water-in-oil type impregnation solution C is obtained. The oil phase is prepared by adding the surfactant glyceryl monostearate to the silicone oil and heating it to 80°C until the silicone oil melts, thus obtaining the oil phase.

[0090] (1) Preparation of modified activated carbon:

[0091] (1-1) A dispersing agent (42.0 g silica sol, silica content of 30%) was prepared with 376 mL of impregnation solution B to form an impregnation solution. 297.0 g of high-temperature activated carbon was saturated and impregnated. In the first active metal impregnation solution, the mass content of nickel as oxide was 3.60%, and the mass content of dispersing agent as silica was 3.72%. After impregnation, the sample was dried at 120 °C for 6 h and calcined at 550 °C for 3 h to obtain the modified activated carbon precursor.

[0092] (1-2) The modified activated carbon precursor obtained above was mixed with 3.5g of alkaline additive (NaOH), ground (particle size after grinding was 5.0μm), and dried at 140℃ for 5h to obtain modified activated carbon;

[0093] (2) 364.6g of pseudoboehmite (alumina mass content of 72.0%), 37.5g of modified activated carbon obtained in step (1), 5.47g of nitric acid, 8.0g of guar gum powder, and 360.0g of deionized water were mixed and kneaded, then extruded into a four-leaf clover shape, and then dried at 150℃ for 5h and calcined at 700℃ for 4h to obtain carrier C;

[0094] (3) Carbon coating treatment was applied to the surface of carrier C using a mixed solution containing polyimide and hydroxymethyl cellulose. The mass content of polyimide in the mixed solution was 9.0%, and the mass content of hydroxymethyl cellulose was 1.5%. The ratio of the volume of the mixed solution (mL) to that of carrier C (g) was 1.5 mL / g. After drying at 180℃ for 6 h, the calcination conditions were: calcination at 650℃ for 5 h under a nitrogen atmosphere. After calcination, a three-dimensional network structure film was formed on the surface of carrier C, resulting in carrier D.

[0095] (4) Impregnate the carrier D obtained in step (3) with impregnation solution C in a saturated impregnation manner, let it stand for 18 hours, and then add fatty alcohol polyoxyethylene ether (structure RO-(CCO)). x -H, where R is a straight-chain alkyl group with 12 carbon atoms and x is 5), is used in an amount of 3.5% of the impregnation solution mass. Then, it is ultrasonically treated for 30 minutes at a frequency of 25 kHz. During the treatment, the material temperature is 70°C, allowing the aqueous phase to separate from the oil phase, while the oil phase gradually accumulates. After phase separation, it is dried at 120°C for 6 hours. The calcination adopts a two-stage calcination process. The first stage calcination temperature is 400°C, the calcination time is 4 hours, and the calcination atmosphere is air. The second stage calcination temperature is 650°C, the calcination time is 6 hours, and the calcination atmosphere is nitrogen.

[0096] The residue hydrodemetallization catalyst CAT-1 was obtained. The physicochemical properties and composition of the catalyst are shown in Table 1.

[0097] Example 2

[0098] Similar to Example 1, except that in step (0), the process of preparing the impregnation solution is as follows:

[0099] In this example, the surfactant is glyceryl distearate, the silicone oil is ethyl silicone oil, and the mass ratio of surfactant to silicone oil is 1.2:8. The co-emulsifier is octadecyl alcohol, 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 gelatin. The mass ratio of co-emulsifier (calculated as molybdenum oxide), phosphorus source (calculated as phosphorus oxide), nickel source (calculated as nickel oxide), and water-soluble polymer to water is 24:267.1:53.4:64.1:90.3:400. The mass ratio of the aqueous phase to the oil phase is 0.8.

[0100] (0-1) Add the co-emulsifier octadecyl alcohol, molybdenum oxide, and phosphoric acid to deionized water in that order. Use a reflux condenser during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 600 r / min. When the temperature is raised to 120°C, maintain this temperature for 4 hours. Maintain a constant stirring speed until a clear solution is obtained. Add basic nickel carbonate to the obtained clear solution to obtain an active metal impregnation solution (MoO3 concentration is 48.78 g / 100 mL, NiO concentration is 11.71 g / 100 mL, and P2O5 concentration is 9.76 g / 100 mL). Divide the solution into impregnation solution A and impregnation solution B at a volume ratio of 7:10.

[0101] (0-2) Water-soluble polymer gelatin is added to the impregnation solution A obtained in step (0-1) to obtain an aqueous phase. The aqueous phase is then added dropwise to the oil phase. During the dropwise addition, the temperature of the oil phase is maintained at 70°C, and stirring is performed simultaneously. The shear homogenization speed is 15000 rpm, the shear homogenization time is 6 min, and the temperature during the shear homogenization process is 75°C. After the droplets are dispersed into an emulsion, a water-in-oil type impregnation solution C is obtained. The oil phase is prepared by adding the surfactant glyceryl monostearate to the silicone oil and heating it to 70°C until the silicone oil melts, thus obtaining the oil phase.

[0102] The residue oil hydrodemetallization catalyst CAT-2 was obtained. The physicochemical properties and composition of the catalyst are shown in Table 1.

[0103] Example 3

[0104] Similar to Example 1, except that in step (0), the process of preparing the impregnation solution is as follows:

[0105] In this example, the surfactant is glyceryl monolaurate, the silicone oil is phenyl silicone oil, and the mass ratio of surfactant to silicone oil is 1.4:8. 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 28:267.1:53.4:64.1:111.3:400. The mass ratio of the aqueous phase to the oil phase is 1.0.

[0106] (0-1) Add the co-emulsifier propylene glycol, molybdenum oxide, and phosphoric acid to deionized water in that order. Use a reflux condenser during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 700 r / min. When the temperature is raised to 120°C, maintain this temperature for 4 hours. Maintain a constant stirring speed until a clear solution is obtained. Add basic nickel carbonate to the obtained clear solution to obtain an active metal impregnation solution (MoO3 concentration is 48.78 g / 100 mL, NiO concentration is 11.71 g / 100 mL, and P2O5 concentration is 9.76 g / 100 mL). Divide the solution into impregnation solution A and impregnation solution B at a volume ratio of 11:10.

[0107] (0-2) Add water-soluble sodium polyacrylate to the impregnation solution A obtained in step (0-1) to obtain an aqueous phase; add the obtained aqueous phase dropwise to the oil phase, maintaining the temperature of the oil phase at 70°C during the dropwise addition process, while stirring, with a shear homogenization rate of 11000 rpm, a shear homogenization time of 7 min, and a temperature of 80°C during the shear homogenization process. After the droplets are dispersed into an emulsion state, a water-in-oil type impregnation solution C is obtained; wherein, the oil phase is prepared by adding the surfactant glyceryl monostearate to the silicone oil, heating to 70°C, and waiting for the silicone oil to melt to obtain the oil phase.

[0108] The residue oil hydrodemetallization catalyst CAT-3 was obtained. The physicochemical properties and composition of the catalyst are shown in Table 1.

[0109] Example 4

[0110] Similar to Example 1, except that in step (0), the process of preparing the impregnation solution is as follows:

[0111] In this example, the surfactant is a polyoxyethylene ether fatty alcohol (structure RO-(CCO)). x -H, where R is a 12-carbon straight-chain alkyl group, x is 5), silicone oil is methylphenyl silicone oil, surfactant to silicone oil mass ratio is 2.5:8, co-emulsifier is n-butanol, molybdenum source is molybdenum oxide, phosphorus source is phosphoric acid, nickel source is basic nickel carbonate, water-soluble polymer is gum arabic, co-emulsifier: molybdenum source (calculated as molybdenum oxide): phosphorus source (calculated as phosphorus oxide): nickel source (calculated as nickel oxide): water-soluble polymer: water mass ratio is 28:267.1:53.4:64.1:51.3:400. The mass ratio of aqueous phase to oil phase is 0.6.

[0112] (0-1) Add the co-emulsifier n-butanol, molybdenum oxide, and phosphoric acid to deionized water in that order. Use a reflux condenser during the reaction. The reaction starts at 28°C. During the reaction, the stirring speed is 400 r / min. When the temperature is raised to 120°C, maintain this temperature for 4 hours. Maintain a constant stirring speed until a clear solution is obtained. Add basic nickel carbonate to the obtained clear solution to obtain an active metal impregnation solution (MoO3 concentration is 48.78 g / 100 mL, NiO concentration is 11.71 g / 100 mL, and P2O5 concentration is 9.76 g / 100 mL). Divide the solution into impregnation solution A and impregnation solution B at a volume ratio of 3:2.

[0113] (0-2) Water-soluble polymer gum arabic is added to the impregnation solution A obtained in step (0-1) to obtain an aqueous phase. The aqueous phase is then added dropwise to the oil phase. During the dropwise addition, the temperature of the oil phase is maintained at 45°C while stirring is performed. The shear homogenization rate is 14000 rpm, the shear homogenization time is 4 min, and the temperature during the shear homogenization process is 50°C. After the droplets are dispersed into an emulsion, a water-in-oil type impregnation solution C is obtained. The oil phase is prepared by adding the surfactant glyceryl monostearate to the silicone oil and heating it to 65°C until the silicone oil melts, thus obtaining the oil phase.

[0114] The residue hydrodemetallization catalyst CAT-4 was obtained. The physicochemical properties and composition of the catalyst are shown in Table 1.

[0115] Example 5

[0116] Similar to Example 1, except that in step (3), the carrier C is subjected to surface carbon coating treatment using a mixed solution containing polyimide and hydroxymethyl cellulose. The mass content of polyimide in the mixed solution is 12.0%, and the mass content of hydroxymethyl cellulose is 2.5%. The ratio of the volume of the mixed solution (mL) to the mass of the carrier C (g) is 1.2 mL / g. After drying at 180°C for 6 hours, the calcination conditions are: calcination at 550°C for 6 hours under a nitrogen atmosphere. After calcination, a three-dimensional network structure film can be formed on the surface of the carrier C, thus obtaining the carrier D.

[0117] The residue oil hydrodemetallization catalyst CAT-5 was prepared. The physicochemical properties and composition of the catalyst are shown in Table 1.

[0118] Example 6

[0119] Similar to Example 1, except that in step (4), the carrier obtained in step (3) is impregnated with impregnation solution C in a saturated impregnation manner, left to stand for 18 hours, and then fatty alcohol polyoxyethylene ether (structure RO-(CCO)) is added. x-H, where R is a straight-chain alkyl group with 12 carbon atoms and x is 5), is used in an amount of 4.5% of the impregnation solution mass. Then, it is ultrasonically treated for 40 min at a frequency of 30 kHz. During the treatment, the material temperature is 60℃, allowing the aqueous phase to separate from the oil phase, while the oil phase gradually accumulates. After phase separation, it is dried at 120℃ for 6 h. The calcination adopts a two-stage calcination process. The first stage calcination temperature is 450℃, the calcination time is 3 h, and the calcination atmosphere is air. The second stage calcination temperature is 600℃, the calcination time is 5 h, and the calcination atmosphere is nitrogen.

[0120] The residue oil hydrodemetallization catalyst CAT-6 was obtained. The physicochemical properties and composition of the catalyst are shown in Table 1.

[0121] Example 7

[0122] Similar to Example 1, except that in step (2), 370.4g of boehmite (alumina mass content of 72.0%), 33.3g of modified activated carbon obtained in step (1), 6.25g of nitric acid, 6.0g of guar gum powder, and 340.0g of deionized water are mixed and kneaded, then extruded into a four-leaf clover shape, dried at 120°C for 6h, and calcined at 650°C for 4h to obtain carrier C.

[0123] The residue oil hydrodemetallization catalyst CAT-7 was obtained. The physicochemical properties and composition of the catalyst are shown in Table 1.

[0124] Comparative Example 1

[0125] Similar to Example 1, except that in step (3), the carrier C is not subjected to surface carbon coating treatment.

[0126] The dCAT-1 catalyst for hydrodemetallization of residue oil was prepared. The physicochemical properties of the catalyst are shown in Table 2.

[0127] Comparative Example 2

[0128] Similar to Example 1, except that the solution used in the carbon coating process in step (3) is changed to a polyimide solution with a mass percentage of 9.0%, and the amount of polyimide solution (in mL) to carrier C (in g) is 1.5 mL / g.

[0129] The dCAT-2 catalyst for hydrodemetallization of residue oil was prepared. The physicochemical properties of the catalyst are shown in Table 2.

[0130] Example 3

[0131] Similar to Example 1, except that no water-soluble polymer was added to the impregnation solution A in step (0-2).

[0132] A hydrodemetallization catalyst dCAT-3 for residue oil was prepared. The physicochemical properties of the catalyst are shown in Table 2.

[0133] Comparative Example 4

[0134] 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 3.5:8, 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, and the water-soluble polymer is carboxymethyl cellulose. 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 20:267.1:53.4:64.1:35.2:400. The mass ratio of the aqueous phase to the oil phase is 0.9.

[0135] The steps for preparing the impregnation solution in this example are as follows:

[0136] (a) Molybdenum oxide and phosphoric acid were added to deionized water in sequence. A reflux condenser was used during the reaction. The reaction started at 28°C. During the reaction, the stirring speed was 500 r / min. When the temperature was raised to 120°C, it was maintained for 4 hours. A constant stirring speed was maintained until a clear solution was obtained. Basic nickel carbonate was added to the obtained clear solution to obtain an active metal impregnation solution. The solution was divided into impregnation solution A and impregnation solution B at a volume ratio of 1:1.

[0137] (b) The surfactant glyceryl monostearate, silicone oil, co-emulsifier cetyl alcohol, and carboxymethyl cellulose were added to the aqueous phase (impregnation solution A) while stirring. The shear homogenization rate was 13,000 rpm, the shear homogenization time was 6 min, and the temperature during the shear homogenization process was 70°C. After the droplets were dispersed into an emulsion, a water-in-oil impregnation solution C was obtained.

[0138] The dCAT-4 catalyst for hydrodemetallization of residue oil was prepared. The physicochemical properties of the catalyst are shown in Table 2.

[0139] Comparative Example 5

[0140] Same as Example 1, except that no ultrasonic treatment was used in step (3).

[0141] The dCAT-5 catalyst for hydrodemetallization of residue oil was prepared. The physicochemical properties of the catalyst are shown in Table 2.

[0142] Comparative Example 6

[0143] Similar to Example 1, except that in step (3), the ultrasonic frequency is 10kHz, the material temperature is 30℃, and the processing time is 10min.

[0144] A hydrodemetallization catalyst dCAT-6 for residue oil was prepared. The physicochemical properties of the catalyst are shown in Table 2.

[0145] Table 1. Physicochemical properties of the catalysts obtained in the examples.

[0146]

[0147] Table 2. Physicochemical properties of the catalysts obtained in the comparative examples

[0148]

[0149] Evaluation test

[0150] The activity and stability tests of the obtained residue hydrodemetallization catalysts were conducted in a 200 mL fixed-bed hydrotreating test apparatus. All catalysts used were strip-shaped with a length of 2-3 mm. The reaction conditions were: reaction temperature 380℃, 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, after 1500 hours of reaction, the demetallization rate was 100% as shown in Example 1, while the others were relative demetallization rates. The demetallization rates (Ni+V) of each catalyst are shown in Tables 4-5, and the properties of the feedstock oil are shown in Table 3.

[0151] Table 3 Properties of Feed Oil

[0152]

[0153]

[0154] Table 4. Catalyst test results obtained in the examples.

[0155]

[0156] Table 5. Test results of catalysts obtained in the comparative examples.

[0157] Comparative numbering Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Catalyst number dCAT-1 dCAT-2 dCAT-3 dCAT-4 dCAT-5 dCAT-6 Relative demetallization rate, % 94.2 94.6 94.3 93.7 93.4 93.1

[0158] As can be seen from Tables 1-5, 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 hydrogenation demetallization catalyst, comprising the following steps: (0) Preparation of the impregnation solution: (0-1) Prepare an aqueous solution of an active metal containing Group VIB metals and Group VIII metals and optional additives as impregnation solution B; (0-2) Add a water-soluble polymer to an aqueous solution containing a group VIB metal, a group VIII metal, and an optional additive, i.e., impregnation A, to obtain an aqueous phase. Add the aqueous phase dropwise to the oil phase to obtain impregnation solution C. (1) Activated carbon was impregnated with impregnation solution B to obtain modified activated carbon; (2) Mix the pseudoboehmite, the modified activated carbon obtained in step (1), and the adhesive, shape them, and calcine them to obtain carrier C; (3) The carrier C obtained in step (2) is subjected to surface carbon coating treatment and calcined to obtain carrier D; (4) The carrier D obtained in step (3) is impregnated with impregnation solution C, a polyether-type nonionic surfactant is added, and the catalyst is obtained by ultrasonic treatment and calcination.

2. The preparation method according to claim 1, characterized in that, Methods for preparing impregnation solutions include: (0-1) Divide the aqueous solution containing Group VIB metals and Group VIII metals and optional additives into two portions, labeled as aqueous phase impregnation solution A and aqueous phase impregnation solution B, respectively. (0-2) Add water-soluble polymer to the aqueous phase impregnation solution A obtained in step (0-1) to obtain an aqueous phase. Add the aqueous phase dropwise to the oil phase to obtain impregnation solution C.

3. The preparation method according to claim 2, characterized in that, In step (0-1) or step (0-2), preferably, the co-emulsifier, the Group VIB metal source, water, and optional auxiliary agent source are first mixed and heated to obtain a clear solution. Then, the Group VIII metal source is added to the clear solution to obtain an aqueous solution containing the active metal, i.e., impregnation solution A or impregnation solution B.

4. The preparation method according to claim 3, characterized in that, The co-emulsifier is selected from one or more of hexadecyl alcohol, octadecyl alcohol, propylene glycol, n-butanol, ethylene alcohol, and glycerol; preferably, the amount of the co-emulsifier is 0.5% to 5.0% of the mass of the resulting aqueous solution containing active metal.

5. The preparation method according to claim 3, characterized in that, The group VIB metal is Mo and / or W; the group VIII metal is Ni and / or Co; the additive is at least one of fluorine, phosphorus, silicon or boron, preferably phosphorus; Preferably, in the aqueous solution containing the active metal, the concentration of Group VIB metals as oxides is 8-75 g / 100 mL, more preferably 10-60 g / 100 mL, the concentration of Group VIII metals as oxides is 2-55 g / 100 mL, more preferably 5-30 g / 100 mL, and the mass concentration of the auxiliaries as oxides is 0-18.0 g / 100 mL, more preferably 0.20-17.0 g / 100 mL.

6. The preparation method according to claim 3, characterized in that, The temperature is heated to 90–120°C.

7. The preparation method according to claim 1 or 2, characterized in that, The volume ratio of impregnation solution A to impregnation solution B is 0.2 to 3.0, preferably 0.3 to 1.

8.

8. The preparation method according to claim 1 or 2, characterized in that, In step (0-2), the water-soluble polymer is one or more of polyvinyl alcohol, carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate; preferably, the mass concentration of the water-soluble polymer in the aqueous phase is 4.0% to 14.0%.

9. The preparation method according to claim 1 or 2, characterized in that, A surfactant is added to the oil, and the mixture is heated to obtain the oil phase. And / or, the surfactant is selected from one or more of glyceryl monostearate, glyceryl distearate, glyceryl monolaurate, and polyoxyethylene ether fatty alcohol; the oil is at least one of silicone oil and vegetable oil; 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; the vegetable oil is selected from one or more of peanut oil, coconut oil, and tea seed oil; preferably, the mass ratio of the surfactant to the oil is 1.0:0.1 to 10, more preferably 1.0:2 to 10; And / or, the heating to a temperature of 45–85°C.

10. The preparation method according to claim 1 or 2, characterized in that, In step (0-2), the mass ratio of the aqueous phase to the oil phase is 0.4-1.8:1.0, preferably 0.5-1.5:1.

0.

11. The preparation method according to claim 1 or 2, characterized in that, In steps (0-2), the aqueous phase is added dropwise to the oil phase and then stirred and sheared to homogenize it. Preferably, the stirring-shear homogenization process involves a stirring speed of 10,000–18,000 rpm, a shear homogenization time of 3–8 min, and a temperature of 50–85°C.

12. The preparation method according to claim 1, characterized in that, In step (1), the method for preparing modified activated carbon includes: (1-1) Impregnate activated carbon with impregnation solution B containing dispersant, dry and calcine to obtain modified activated carbon precursor; (1-2) The modified activated carbon precursor obtained in step (1-1) is mixed with an alkaline additive, ground and dried to obtain modified activated carbon.

13. The preparation method according to claim 13, characterized in that, In step (1-1), the dispersing agent is silica sol; preferably, the silica sol contains 20.0% to 50.0% silica by mass. And / or, in impregnation solution B, the dispersing agent has a mass content of 0.5% to 5.0% based on silica.

14. The preparation method according to claim 13, characterized in that, In step (1-2), the alkaline additive is one or more of sodium hydroxide, potassium hydroxide, and sodium carboxylate; preferably, the mass ratio of the alkaline additive to the activated carbon used in step (1-1) is 0.01 to 0.

10.

15. The preparation method according to claim 1, characterized in that, In step (2), the alumina content in the pseudoboehmite is 65.0% to 80.0% by mass; And / or, in step (2), the adhesive is an inorganic acid and / or an organic acid, wherein the inorganic acid is one or more of nitric acid, sulfuric acid, boric acid, and phosphoric acid, and the organic acid is one or more of tartaric acid, citric acid, and oxalic acid; preferably, the mass fraction of the adhesive is 0.5% to 5.0% of the total mass of boehmite (calculated as alumina) and modified activated carbon.

16. The preparation method according to claim 1, characterized in that, In step (3), the carbon coating treatment uses a mixed solution of carbon-containing precursor and water-soluble cellulose; preferably, the carbon-containing precursor is one or more of polyimide, polyfurfuryl alcohol, phenolic resin, etc., and the water-soluble cellulose is one or more of hydroxymethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, etc.

17. The preparation method according to claim 16, characterized in that, In the mixed solution, the mass content of the carbon-containing precursor is 8.0% to 16.0%, and the mass content of the water-soluble cellulose is 0.5% to 3.5%. And / or, in step (3), the amount of the mixed solution in mL and the amount of carrier C in g are 0.8 to 1.5 mL / g.

18. The preparation method according to claim 1, characterized in that, In step (4), the surfactant is a fatty alcohol polyoxyethylene ether; preferably, the amount of the surfactant is 2.5% to 7.5% of the mass of the impregnation solution C.

19. The preparation method according to claim 1, characterized in that, In step (4), the ultrasonic treatment conditions are as follows: the ultrasonic frequency is 15-35 kHz, the material temperature is 35-75 ℃, and the time is 15-60 min.

20. The preparation method according to claim 1, characterized in that, The roasting process employs a two-stage roasting process. The first stage roasting temperature is 350–450℃, the roasting time is 2–6 hours, and the roasting atmosphere is one or more of air, nitrogen, or water vapor, preferably air. The second stage roasting temperature is 450–750℃, the roasting time is 2–8 hours, and the roasting atmosphere is one or more of air, nitrogen, or water vapor, preferably nitrogen. Preferably, the second-stage roasting temperature is 150–250°C higher than the first-stage roasting temperature.

21. The hydrogenation demetallization catalyst obtained by any of the preparation methods described in claims 1-20.

22. The catalyst according to claim 21, characterized in that, The catalyst includes a support and a second active metal. The support includes alumina, activated carbon and a first active metal, wherein the mass ratio of alumina to activated carbon is 4.0 to 12.0:1, preferably 6.0 to 9.0:

1.

23. The catalyst according to claim 22, characterized in that, The first active metal includes at least one group VIB metal and at least one group VIII metal, wherein the group VIB metal is preferably molybdenum and the group VIII metal is preferably nickel; the second active metal includes at least one group VIB metal and at least one group VIII metal, wherein the group VIB metal is preferably molybdenum and the group VIII metal is preferably nickel.

24. The catalyst according to claim 23, characterized in that, In the catalyst, based on the mass of the catalyst, the content of group VIB metal oxides is 9.0% to 35.0%, and the content of group VIII metal oxides is 5.0% to 16.0%. Preferably, based on the total mass of Group VIII metal oxides in the catalyst, the content of Group VIII metal oxides in the first active component is 35% to 60%, and the content of Group VIII metal oxides in the second active component is 40% to 65%. Preferably, based on the total mass of Group VIB metal oxides in the catalyst, the content of Group VIB metal oxides in the first active component is 35% to 60%, and the content of Group VIB metal oxides in the second active component is 40% to 65%.

25. The catalyst according to claim 22, characterized in that, The catalyst has a specific surface area of ​​150–180 m². 2 / g, with a pore volume of 0.60–0.90 mL / g; preferably, the catalyst has a specific surface area of ​​160–175 m² / g. 2 / g, with a pore volume of 0.70~0.85mL / g.

26. The catalyst according to claim 22, characterized in that, The catalyst includes an auxiliary component, which is selected from at least one of fluorine, phosphorus, silicon or boron, preferably phosphorus; Preferably, in the catalyst, the content of the auxiliary component, calculated as oxide, is 2.0% to 8.0% based on the mass of the catalyst.

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