A method for preparing a hydrogenation catalyst

Abstract

The application discloses a preparation method of a hydrogenation catalyst. The method comprises the following steps: (1) preparing an oil phase by mixing a surfactant and oil; (2) uniformly mixing a co-emulsifier, a group-VIB metal source, water and an optional phosphorus source to prepare a clear solution; (3) adding a group-VIII metal source into the clear solution to obtain an impregnation solution, which is divided into two parts, namely, impregnation solution A and impregnation solution B; (4) adding a water-soluble polymer into the impregnation solution A to obtain an aqueous phase; (5) adding the aqueous phase into the oil phase in the form of liquid drops, and shearing and homogenizing to obtain impregnation solution C; (6) mixing and kneading a carrier dry glue powder and the impregnation solution B, shaping, drying, and roasting to obtain a catalyst intermediate; and (7) impregnating the catalyst intermediate with the impregnation solution C, standing, then adding a polyether non-ionic surfactant, ultrasonic treatment, drying, and roasting to obtain the hydrogenation catalyst. The residue oil hydrogenation metal catalyst prepared by using the impregnation solution disclosed by the application can improve the hydrogenation activity and stability of the catalyst.

Description

Technical Field

[0001] This invention relates to a method for preparing a hydrogenation impregnation solution and a hydrogenation catalyst. Background Technology

[0002] The global trend of crude oil becoming increasingly heavy and of lower quality is intensifying, while market demand for light oil products is also growing rapidly. Heavy oil hydrotreating technology is gradually becoming a focus of attention in the petrochemical industry. Fixed-bed residue hydrotreating technology has a wide range of applications and is an important means to achieve clean and efficient utilization of vacuum residue. However, due to the presence of metals and other heteroatoms in the residue, the hydrotreating catalyst is prone to deactivation during the reaction process due to the deposition of metals and carbon deposits. Since the demetallization catalyst occupies a relatively prominent position in the fixed-bed residue hydrotreating catalyst gradation system and bears a greater reaction load, it is crucial to develop a hydrotreating catalyst with a longer lifespan and better hydrotreating performance.

[0003] CN102600913A discloses a method for preparing an aqueous solution for impregnation of molybdenum, nickel, and phosphorus. The method involves first preparing an aqueous solution of molybdenum, nickel, and phosphorus that can be dissolved, then adding a complex or organic acid. After complete dissolution, the remaining nickel is added, and the mixture is heated to boiling until completely dissolved. This preparation method has the advantages of adjustable molybdenum-nickel ratio, simple preparation process, large dissolution capacity, and long stability time. It can be used to prepare impregnation solutions for hydrogenation catalysts.

[0004] CN105709765A This invention 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] CN104646007A discloses a residue oil hydrodemetallization catalyst and its preparation and application. First, an activated carbon support undergoes two pretreatment processes: hydrochloric acid washing and nitric acid oxidation. Then, a composite additive, activated carbon, and alumina are mixed and extruded to prepare an activated carbon / alumina composite. Finally, metal is loaded onto the support using a hydrotalcite method, i.e., an equal volume of a mixed solution of terephthalic acid, nickel nitrate, urea, and ammonium nitrate in a molar ratio of 2:1:(2.5-5):(1-5) is impregnated, crystallized, washed several times, and dried to obtain nickel salt talc microcrystals. These microcrystals are then placed in a Mo salt solution for complete displacement, filtered, washed, and dried to obtain green solid particles, which are then calcined to obtain the residue oil hydrodemetallization catalyst.

[0006] CN112619677A discloses a method for preparing a catalyst for supplemental refining of lubricating oil through hydrogenation. The method includes the following steps: providing a porous catalyst support containing alumina; preparing an additive solution and impregnating and drying the catalyst support to obtain support A; preparing a Mo-Ni-P solution and a W-Ni solution required for the catalyst composition; adding an oil phase, a surfactant, and a co-surfactant to the Mo-Ni-P solution or the W-Ni solution, stirring, and mixing evenly to obtain a water-in-oil microemulsion; impregnating support A with the microemulsion, followed by drying and calcination to obtain a catalyst semi-finished product; impregnating the catalyst semi-finished product with the W-Ni solution or the Mo-Ni-P solution, followed by drying and calcination to obtain the catalyst for supplemental refining of lubricating oil through hydrogenation.

[0007] CN101757954A discloses a method for preparing supported selective hydrogenation catalysts using microemulsion technology. To improve the hydrogenation activity and selectivity of the catalyst, this method prepares a microemulsion system containing surfactants, co-surfactants, an oil phase, and a soluble metal salt solution in a constant-temperature water bath. The components of this microemulsion system are prepared in a specific ratio, and no significant permeation occurs; it is a microemulsion system with high and stable interfacial film strength.

[0008] Currently, in the field of residue oil hydrotreating catalysts, the impregnation method used in catalyst preparation is still mainly aqueous solution impregnation, which involves single-phase impregnation by dispersing the metal in an aqueous solution. Due to the influence of the impregnation process's spray angle and wetting conditions, the dispersion of the active metal on the catalyst surface is limited. Although multiphase impregnation methods are also used, the dispersion of the active metal in the resulting catalyst still needs improvement. The degree of active metal dispersion directly affects the catalyst's performance. Therefore, it is necessary to further optimize the impregnation method of the active metal by improving the catalyst preparation method, thereby further improving the catalyst's hydrotreating activity and stability. Summary of the Invention

[0009] To address the shortcomings of existing technologies, this invention provides a method for preparing a hydrogenation catalyst. The hydrogenation catalyst prepared using this method, particularly a metal catalyst for residue oil hydrogenation, can improve the catalyst's hydrogenation activity and stability.

[0010] The first aspect of this invention provides a method for preparing a hydrogenation catalyst, comprising:

[0011] (1) Add the surfactant to the oil and heat it to obtain the oil phase;

[0012] (2) Mix the co-emulsifier, the Group VIB metal source, water, and optionally the phosphorus source evenly, and heat until a clear solution is obtained;

[0013] (3) Add the Group VIII metal source to the clear solution obtained in step (2) to obtain an active metal impregnation solution. Divide the above impregnation solution into two parts and label them as impregnation solution A and impregnation solution B respectively.

[0014] (4) Add water-soluble polymer to the impregnation solution A obtained in step (3) to obtain an aqueous phase;

[0015] (5) The aqueous phase from step (4) is added dropwise to the oil phase obtained in step (1) while the oil phase remains liquid during the dropwise addition. Simultaneously, stirring and shearing are performed to homogenize the liquid to obtain the impregnation solution C.

[0016] (6) Mix the dry adhesive powder of the carrier and the impregnation liquid B in step (3), shape it, and then dry and calcinate it to obtain the catalyst intermediate.

[0017] (7) Impregnate the catalyst intermediate obtained in step (6) with impregnation solution C, let it stand, then add polyether-type nonionic surfactant, then sonicate, dry and calcine to obtain hydrogenation catalyst.

[0018] In step (1), 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.

[0019] In step (1), the temperature is heated to 40-80°C to make the oil phase appear as a uniform liquid.

[0020] In step (1), the mass ratio of the added surfactant to the mass of oil is 1.0:0.1 to 10, preferably 1.0:2 to 10.

[0021] In step (2), the co-emulsifier is selected from one or more of polyethylene glycol-8000, polyethylene glycol-400, cetyl alcohol, octadecanol, propylene glycol, n-butanol, polyvinyl alcohol and glycerin.

[0022] In step (2), the amount of the co-emulsifier is 0.5% to 5.0% of the mass of the aqueous phase obtained in step (4).

[0023] In step (2), 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 phosphorus source may be one or more of phosphoric acid, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate. In the active metal impregnation solution in step (3), the mass concentration of phosphorus as oxide is 1.0% to 8.0%.

[0024] In step (2), the water is distilled water or deionized water, and the conductivity of the water should be less than 10.0 mS.

[0025] In step (2), the temperature is heated to 90-120°C to ensure that the substances added in step (2) are mixed evenly to form a clear solution.

[0026] In step (3), 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.

[0027] In step (3), the concentration of Group VIB metals as oxides in the active metal impregnation solution is 8-80 g / 100 ml, preferably 10-60 g / 100 ml, and the concentration of Group VIII metals as oxides is 2-50 g / 100 ml, preferably 5-30 g / 100 ml.

[0028] In step (3), the volume ratio of impregnation solution A to impregnation solution B is 0.1 to 6.0, preferably 0.25 to 5.0.

[0029] In step (4), 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).

[0030] In step (4), the mass concentration of the water-soluble polymer in the aqueous phase is 4.0 to 14.0%.

[0031] In step (5), 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.

[0032] In step (5), the mass ratio of the aqueous phase to the oil phase is 0.4 to 8.0:1.0, preferably 0.5 to 5.0:1.0.

[0033] In step (5), the stirring and shearing homogenization process is carried out at a stirring speed of 10,000 to 18,000 rpm, a shearing homogenization time of 3 to 8 min, and a temperature of 50 to 85°C.

[0034] In step (5), the particle size of the water-in-oil droplets in the impregnation solution C is 5-20 nm.

[0035] In step (6), the carrier dry adhesive powder can be any type of dry adhesive powder commonly used in the art, and can be one or more of the raw materials for preparing alumina, silicon dioxide, titanium dioxide, magnesium oxide, zirconium oxide, or composite carriers, preferably alumina. Materials with different average pore sizes can be selected as needed, and the shape of the formed catalyst is no longer further limited, and can be clover-shaped, trefoil-shaped, cylindrical, etc. During the catalyst forming process, forming aids can be added, such as at least one of adhesive solvent, extrusion aid, and water. Preferably, the carrier dry adhesive powder is a carrier dry adhesive powder for a catalyst used in the hydrodemetallization of residue oil, and the hydrodemetallization catalyst is a catalyst for the hydrodemetallization of residue oil. More preferably, the properties of the carrier dry adhesive powder after high-temperature calcination (i.e., calcination at 450-700℃ for 1-8 hours) are as follows: specific surface area of ​​150-350 m². 2 / g, pore volume 0.3~1.0cm³ 3 / g, the pore volume of pores with a diameter of 10-30 nm accounts for more than 30% of the total pore volume, preferably 40%-80%.

[0036] In step (7), the polyether-type nonionic surfactant is one or more of fatty alcohol polyvinyl chloride ether, ester polyvinyl chloride ether, phenolic polyvinyl chloride ether, and fatty amine polyvinyl chloride ether.

[0037] In step (7), the amount of the polyether-type nonionic surfactant used is 2.5% to 7.5% of the mass of the impregnation solution C.

[0038] In step (7), the impregnation method is a conventional over-impregnation method. The liquid-to-solid volume ratio of the impregnation solution C to the catalyst intermediate is 2.0–8.0. The impregnated sample is left to stand at room temperature for 1–12 hours.

[0039] In step (7), 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.

[0040] In step (7), the drying temperature is 80℃-180℃, and the drying time is 2-8h; the calcination temperature is 450℃-700℃, and the calcination time is 2-8h. The calcination atmosphere is one or more of air, nitrogen, water vapor, etc., preferably an air atmosphere.

[0041] The present invention also provides a hydrogenation catalyst prepared by the above method, particularly a residue oil hydrogenation demetallization catalyst.

[0042] In the hydrogenation catalyst, based on the mass of the hydrogenation catalyst, the content of Group VIB metals as oxides is 6.0% to 26.0%, and the content of Group VIII metals as oxides is 2.0% to 14.0%.

[0043] Compared with the prior art, the present invention has the following beneficial effects:

[0044] Conventional active metal impregnation solutions are all aqueous phases. Active metals tend to aggregate during loading, leading to strong acidity on the support surface, high cracking capacity during the reaction, and limited improvement in the hydrogenation capacity of the active metal. This invention utilizes surfactants to effectively disperse the prepared aqueous phase containing the active metal and the carrier matrix in an oil phase and a dispersion matrix, forming an impregnation solution where the active metal is dispersed within the dispersion matrix via the carrier matrix—a "water-in-oil" type impregnation solution. This impregnation solution is then used to impregnate the catalyst support, resulting in a catalyst with a more uniform distribution of active metals both inside and on the surface of the support. First, this invention uses a co-emulsifier to fully disperse the main active metal in ionic form within the aqueous carrier matrix. Then, a co-metallic metal is dissolved in the solution, yielding an aqueous phase containing both the main metal and the co-metallic metal. To control particle size and maintain particle size distribution during the subsequent formation of the water-in-oil emulsion, a water-soluble polymer is added to the resulting aqueous phase as a "protective layer" for the particles. This water-soluble polymer adsorbs onto the particle surface during the subsequent water-in-oil emulsion formation, forming a surface layer of a certain thickness that effectively hinders particle collisions and aggregation, further improving the system's stability. Then, under specific conditions, the aqueous phase is dispersed in the oil phase to obtain the hydrogenation catalyst impregnation solution.

[0045] This invention employs a two-step method for loading active metals using a water-in-oil emulsion. The active metal emulsion is added during the carrier mixing process and later during the loading process. Introducing the water-in-oil emulsion during mixing helps to initially protect the metal during loading, further reducing the interaction between the metal and the alumina carrier during drying and calcination. Simultaneously, the pores of the carrier are protected during drying and calcination. The later loading of the active metal is achieved using the water-in-oil emulsion. The advantage lies in utilizing the highly dispersed nature of the aqueous phase in the oil phase. The aqueous phase serves as the carrier matrix for the metal components, while the oil phase uniformly disperses the metal from the aqueous phase on the carrier surface and within the pores. In this invention, the water-in-oil droplets can penetrate deep into the pores and surface of the carrier. By introducing a polyether-type nonionic surfactant, the "surface layer" on the surface of the colloidal 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. Finally, after drying and calcining, the impregnated support can be used to obtain a hydrogenation catalyst with more uniform dispersion of active metals.

[0046] When the hydrogenation catalyst impregnation solution of this invention is used to impregnate the hydrodemetallization support of residue oil to prepare a hydrodemetallization catalyst, the catalyst has better dispersion of active metals, and its anti-carbon deposition performance, demetallization activity and metal impurity tolerance are all greatly improved, which can ensure the long-term stable operation of the equipment. Detailed Implementation

[0047] 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.

[0048] Example 1

[0049] 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 1:8. The co-emulsifier is polyethylene glycol-8000, 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 (molecular weight 200,000). 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 20:265:58.5:64.8:35.2:400. The mass ratio of oil phase to water phase and impregnation solution B is 900:880. During the catalyst intermediate forming process, the mass ratio of alumina dry adhesive powder to adhesive solvent is 100:3. During the extrusion process, the water-powder mass ratio is 1.16, where water is diluted impregnation solution B, and the volume ratio of deionized water to impregnation solution B is 5:1.

[0050] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0051] (1) Add the surfactant glyceryl monostearate to the silicone oil, heat to 80°C, and wait for the silicone oil to melt to obtain the oil phase;

[0052] (2) Add the co-emulsifier polyethylene glycol-8000, 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 120°C, the temperature is maintained for 4 hours. The stirring speed is kept constant until a transparent and clear solution is obtained.

[0053] (3) Add basic nickel carbonate to the clear solution obtained in step (2) to obtain an active metal impregnation solution, and divide it into impregnation solution A and impregnation solution B in a volume ratio of 1:1.

[0054] (4) Add water-soluble polymer polyvinyl alcohol to the impregnation solution A obtained in step (3) to obtain an aqueous phase;

[0055] (5) The aqueous phase from step (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 80°C, and stirring is performed simultaneously. The shear homogenization speed 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 impregnation solution C is obtained.

[0056] (6) The properties of alumina dry adhesive powder (after high-temperature calcination: specific surface area of ​​195 m²) 2 / g, pore volume is 0.74cm 3 / g, the pores of 10-30nm in the pore distribution account for 53.6% of the total pore volume), adhesive solvent, deionized water, and impregnation liquid B in step (3). After mixing and molding the above materials, they are dried at 140°C for 4 hours and calcined at 650°C for 3 hours to obtain the catalyst intermediate.

[0057] (7) The catalyst intermediate was impregnated with the impregnation solution C obtained in step (5), and allowed to stand for 18 hours. Then, fatty alcohol polyvinyl chloride ether (R = 12, x = 5) was added at a rate of 3.5% of the impregnation solution mass. The mixture was then ultrasonically treated for 30 minutes at a frequency of 25 kHz. The material temperature during the treatment was 70°C, allowing the aqueous phase to separate from the oil phase, while the oil phase gradually accumulated. After phase separation, the mixture was dried at 120°C for 6 hours and then calcined at 550°C for 4 hours to obtain the residue oil hydrodemetallization catalyst CAT-1. The properties of the obtained impregnation solution and catalyst are shown in Table 1, and the experimental results of the catalyst are shown in Table 4.

[0058] Example 2

[0059] 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 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 24:265:58.5:64.8:45.2:400. The mass ratio of oil phase to water phase and impregnation solution B is 920:903. During the catalyst intermediate forming process, the mass ratio of alumina dry adhesive powder to adhesive solvent is 100:3. During the extrusion process, the water-to-powder ratio is 1.16, where water is diluted impregnation solution B, and the volume ratio of deionized water to impregnation solution B is 5:1.

[0060] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0061] (1) Add the surfactant glyceryl distearate to the silicone oil, heat to 75°C, and wait for the silicone oil to melt to obtain the oil phase;

[0062] (2) Add the co-emulsifier cetyl alcohol, 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 600 r / min. When the temperature is heated to 120°C, the temperature is maintained for 4 hours. The stirring speed is kept constant until a transparent and clear solution is obtained.

[0063] (3) Add basic nickel carbonate to the clear solution obtained in step (2) to obtain an active metal impregnation solution and divide it into impregnation solution A and impregnation solution B at a volume ratio of 1:1;

[0064] (4) Add water-soluble polymer carboxymethyl cellulose to the impregnation solution A obtained in step (3) to obtain an aqueous phase;

[0065] (5) The aqueous phase from step (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 65°C, and stirring is performed simultaneously. The shear homogenization rate is 16000 rpm, the shear homogenization time is 6 min, and the temperature during the shear homogenization process is 70°C. After the droplets are dispersed into an emulsion, a water-in-oil impregnation solution C is obtained.

[0066] (6) Mix the alumina dry adhesive powder (same as in Example 1), adhesive solvent, deionized water, and impregnation liquid B from step (3) to form the above materials. Then, dry them at 140°C for 4 hours and calcine them at 650°C for 3 hours to obtain the catalyst intermediate.

[0067] (7) The catalyst intermediate was impregnated with the impregnation solution C obtained in step (5), and allowed to stand for 18 hours. Then, fatty alcohol polyvinyl chloride ether (R = 12, x = 5) was added at a rate of 4.5% of the impregnation solution mass. The mixture was then ultrasonically treated for 40 minutes at a frequency of 30 kHz. The material temperature during the treatment was 60°C, allowing the aqueous phase to separate from the oil phase, while the oil phase gradually accumulated. After phase separation, the mixture was dried at 120°C for 6 hours and then calcined at 550°C for 4 hours to obtain the residue oil hydrodemetallization catalyst CAT-2. The properties of the obtained impregnation solution and catalyst are shown in Table 1, and the experimental results of the catalyst are shown in Table 4.

[0068] Example 3

[0069] 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 (molecular weight 8000). 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 28:265:58.5:64.8:55.7:400. The mass ratio of oil phase to water phase and impregnation solution B is 940:928. During the catalyst intermediate forming process, the mass ratio of alumina dry adhesive powder to adhesive solvent is 100:3, and the water-to-powder ratio during extrusion is 1.16, where water is diluted impregnation solution B, and the volume ratio of deionized water to impregnation solution is 5:1.

[0070] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0071] (1) Add the surfactant glyceryl monolaurate to the silicone oil, heat to 75°C, and wait for the silicone oil to melt to obtain the oil phase;

[0072] (2) Add the co-emulsifier propylene glycol, 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 700 r / min. When the temperature is heated to 120°C, the temperature is maintained for 4 hours. The stirring speed is kept constant until a transparent and clear solution is obtained.

[0073] (3) Add basic nickel carbonate to the clear solution obtained in step (2) to obtain an active metal impregnation solution, and divide it into impregnation solution A and impregnation solution B in a volume ratio of 1:1.

[0074] (4) Add water-soluble polymer sodium polyacrylate (molecular weight of 8000) to the impregnation solution A obtained in step (3) to obtain an aqueous phase;

[0075] (5) The aqueous phase from step (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°C, and stirring is performed simultaneously. The shear homogenization rate is 17000 rpm, the shear homogenization time is 7 min, and the temperature during the shear homogenization process is 80°C. After the droplets are dispersed into an emulsion, a water-in-oil impregnation solution C is obtained.

[0076] (6) Mix the alumina dry adhesive powder (same as in Example 1), adhesive solvent, deionized water, and impregnation liquid B from step (3) to form the above materials. Then, dry them at 140°C for 4 hours and calcine them at 650°C for 3 hours to obtain the catalyst intermediate.

[0077] (7) The catalyst intermediate was impregnated with the impregnation solution C obtained in step (5), and allowed to stand for 18 hours. Then, fatty alcohol polyvinyl chloride ether (R = 12, x = 5) was added at a concentration of 5.5% of the impregnation solution mass. The mixture was then ultrasonically treated for 50 minutes at a frequency of 20 kHz. The material temperature during the treatment was 50°C, allowing the aqueous phase to separate from the oil phase, while the oil phase gradually accumulated. After phase separation, the mixture was dried at 120°C for 6 hours and then calcined at 550°C for 4 hours to obtain the residue oil hydrodemetallization catalyst CAT-3. The properties of the obtained impregnation solution and catalyst are shown in Table 1, and the experimental results of the catalyst are shown in Table 4.

[0078] Example 4

[0079] In this example, the surfactant is polyoxyethylene ether fatty alcohol (R = 12, x = 5), the silicone oil is methylphenyl silicone oil, and the mass ratio of surfactant to silicone oil is 0.8:8. 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, and the water-soluble polymer is gelatin. 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 28:265:58.5:64.8:25.7:400. The mass ratio of oil phase to water phase and impregnation solution B is 880:856. During the catalyst intermediate forming process, the mass ratio of alumina dry adhesive powder to adhesive solvent is 100:3. During the extrusion process, the water-to-powder ratio is 1.16, where water is diluted impregnation solution B, and the volume ratio of deionized water to impregnation solution is 5:1.

[0080] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0081] (1) Add the surfactant polyoxyethylene ether fatty alcohol to the silicone oil, heat to 70°C, and wait for the silicone oil to melt to obtain the oil phase;

[0082] (2) Add the co-emulsifier n-butanol, 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 400 r / min. When the temperature is heated to 120°C, the temperature is maintained for 4 hours. The stirring speed is kept constant until a transparent and clear solution is obtained.

[0083] (3) Add basic nickel carbonate to the clear solution obtained in step (2) to obtain an active metal impregnation solution, and divide it into impregnation solution A and impregnation solution B in a volume ratio of 1:1.

[0084] (4) Add water-soluble polymer gelatin to the impregnation solution A obtained in step (3) to obtain an aqueous phase;

[0085] (5) The aqueous phase from step (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 45°C, 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 50°C. After the droplets are dispersed into an emulsion, a water-in-oil impregnation solution C is obtained.

[0086] (6) Mix the alumina dry adhesive powder (same as in Example 1), adhesive solvent, deionized water, and impregnation liquid B from step (3) to form the above materials. Then, dry them at 140°C for 4 hours and calcine them at 650°C for 3 hours to obtain the catalyst intermediate.

[0087] (7) The catalyst intermediate was impregnated with the impregnation solution C obtained in step (5), and allowed to stand for 18 hours. Then, fatty alcohol polyvinyl chloride ether (R = 12, x = 5) was added at a concentration of 6.5% of the impregnation solution mass. The mixture was then ultrasonically treated for 20 minutes at a frequency of 15 kHz. The material temperature during the treatment was 40°C, allowing the aqueous phase to separate from the oil phase, while the oil phase gradually accumulated. After phase separation, the mixture was dried at 120°C for 6 hours and then calcined at 550°C for 4 hours to obtain the residue oil hydrodemetallization catalyst CAT-4. The properties of the obtained impregnation solution and catalyst are shown in Table 1, and the test results of the catalyst are shown in Table 4.

[0088] Comparative Example 1

[0089] Similar to Example 1, except that the mass ratio of surfactant to silicone oil in step (1) is 0.64:8. The final catalyst obtained is dCAT-1. The properties of the obtained impregnation solution and catalyst are shown in Table 2, and the test results of the catalyst are shown in Table 5.

[0090] Comparative Example 2

[0091] Similar to Example 1, except that the temperature of the oil phase was 40°C during the dropwise addition of the impregnation solution to the oil phase in step (4) in step (1). The final catalyst obtained was dCAT-2. The properties of the obtained impregnation solution and catalyst are shown in Table 2, and the test results of the catalyst are shown in Table 5.

[0092] Comparative Example 3

[0093] Similar to Example 1, except that the ultrasonic frequency in step (5) was 10 kHz, the material temperature was 30 °C, and the reaction time was 10 min. The final catalyst obtained was dCAT-3. The properties of the obtained impregnation solution and catalyst are shown in Table 2, and the test results of the catalyst are shown in Table 5.

[0094] Comparative Example 4

[0095] Instead of using the method of this invention, compared with Example 1, an aqueous solution containing molybdenum, nickel, and phosphorus was directly used as the impregnation solution (molybdenum source: molybdenum oxide, phosphoric acid source: phosphoric acid, and basic nickel carbonate source) to impregnate the support (same as Example 1). After the impregnated catalyst was allowed to stand at room temperature for 18 hours, it was first dried at 120°C for 4 hours and then calcined at 550°C for 4 hours. The final catalyst obtained was dCAT-4. The properties of the obtained impregnation solution and catalyst are shown in Table 2, and the test results of the catalyst are shown in Table 5.

[0096] Comparative Example 5

[0097] Similar to Example 1, except that no water-soluble polymer was added to the mixture (from step (3)) in step (4). The final catalyst obtained was dCAT-5. The properties of the obtained impregnation solution and catalyst are shown in Table 2, and the test results of the catalyst are shown in Table 5.

[0098] Comparative Example 6

[0099] 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 1:8. The co-emulsifier is polyethylene glycol-8000, the molybdenum source is molybdenum oxide, the phosphorus source is phosphoric acid, and the nickel source is basic nickel carbonate. 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 is 20:265:58.5:64.8:400. The mass ratio of oil phase to water phase and impregnation solution B is 900:880. During the catalyst intermediate forming process, the mass ratio of alumina dry adhesive powder to adhesive solvent is 100:3. During the extrusion process, the water-powder mass ratio is 1.16, where water is diluted impregnation solution B, and the volume ratio of deionized water to impregnation solution B is 5:1.

[0100] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0101] (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 120°C, the temperature is maintained for 4 hours. The stirring speed is kept constant until a clear solution is obtained.

[0102] (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 and impregnation solution B in a volume ratio of 1:1.

[0103] (3) Add the surfactant glyceryl monostearate, silicone oil, and co-emulsifier polyethylene glycol-8000 to impregnation solution A, while stirring. The shear homogenization speed is 15000 rpm, the shear homogenization time is 5 min, and the temperature during the shear homogenization process is 60℃. After the droplets are dispersed into an emulsion, a water-in-oil type impregnation solution C is obtained.

[0104] (4) Mix the alumina dry adhesive powder (same as in Example 1), adhesive solvent, deionized water, and impregnation liquid B from step (2) with the above materials, knead and shape them, dry them at 140°C for 4 hours, and calcine them at 650°C for 3 hours to obtain the catalyst intermediate.

[0105] (5) The catalyst intermediate was impregnated with the impregnation solution C obtained in step (3), allowed to stand for 18 hours, dried at 120°C for 6 hours, and calcined at 550°C for 4 hours to obtain the residue oil hydrodemetallization catalyst dCAT-6. The properties of the impregnation solution and the catalyst are shown in Table 2, and the test results of the catalyst are shown in Table 5.

[0106] Comparative Example 7

[0107] Similar to Example 1, except that no ultrasonic treatment was used in step (6). The final catalyst obtained was dCAT-7. The properties of the obtained impregnation solution and catalyst are shown in Table 2, and the test results of the catalyst are shown in Table 5.

[0108] Table 1. Physicochemical properties of the impregnation solutions and catalysts obtained in each embodiment.

[0109]

[0110]

[0111] Table 2. Physicochemical properties of the impregnation solutions and catalysts obtained in each comparative example.

[0112] Serial Number Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Droplet particle size / nm 10～80 10～80 10～80 - 10～80 10～80 - Catalyst number dCAT-1 dCAT-2 dCAT-3 dCAT-4 dCAT-5 dCAT-6 dCAT-7 <![CDATA[Specific surface area, m 2 / g]]> 159 156 154 158 152 150 151 <![CDATA[Pore volume, cm 3 / g]]> 0.53 0.57 0.54 0.51 0.47 0.52 0.48 Metal content <![CDATA[MoO3,wt%]]> 12.4 12.2 12.3 12.0 12.2 12.1 12.0 NiO, wt% 2.6 2.5 2.4 2.6 2.5 2.7 2.6 Additive content <![CDATA[P2O5,wt%]]> 3.1 2.9 2.8 3.2 3.0 3.2 3.0 Metal Dispersion <![CDATA[I Mo / I Al *100]]> 5.65 5.58 5.47 5.57 5.45 5.56 5.48 <![CDATA[I Ni / I Al *100]]> 1.90 1.86 1.89 1.85 1.82 1.78 1.86

[0113] Application examples

[0114] The activity and stability tests of the residue hydrodemetallization catalysts CAT-1 to CAT-4 and dCAT-1 to dCAT-7 were conducted in a 200 mL fixed-bed hydrotreating experimental setup. All catalysts used were strip-shaped with a length of 2–3 mm. The reaction conditions were: reaction temperature 375 °C, reaction pressure 15.0 MPa, and liquid hourly space velocity 1.0 h⁻¹. -1 With a hydrogen-to-oil volume ratio of 700, after 1200 h of reaction, the demetallization rates (Ni+V) of each catalyst are shown in Tables 4 and 5, and the properties of the feedstock oil are shown in Table 3.

[0115] Table 3 Properties of Feed Oil

[0116] project <![CDATA[Density at 20°C, kg / m 3 > 970.2 S, wt% 2.56 N, wt% 0.48 Ni, μg / g 33.5 V, μg / g 69.4 CCR, wt% 12.8

[0117] Table 4 shows the test results of the catalysts obtained in each example.

[0118]

[0119] Table 5 shows the experimental results of the catalysts obtained in each comparative example.

[0120]

[0121] As can be seen from Tables 1-5, the hydrodemetallization catalyst prepared according to the method of the present invention has a more unobstructed pore structure and a suitable specific surface area. It maintains 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 catalyst, comprising: (1) adding a surfactant to an oil, and heating to obtain an oil phase; (2) mixing an emulsifying assistant, a Group VIB metal source, water, and optionally a phosphorus source, and heating until a clear solution is obtained; (3) adding a Group VIII metal source to the clear solution obtained in step (2) to obtain an active metal impregnation solution, and dividing the impregnation solution into two parts, and marking them as impregnation solution A and impregnation solution B; (4) adding a water-soluble polymer to the impregnation solution A obtained in step (3) to obtain an aqueous phase; (5) adding the aqueous phase obtained in step (4) to the oil phase obtained in step (1) in the form of droplets, and maintaining the oil phase in a liquid state during the adding process, and simultaneously performing stirring and shearing homogenization to obtain an impregnation solution C; (6) mixing and kneading a carrier dry gel powder and the impregnation solution B in step (3), and shaping, and then drying and calcining to obtain a catalyst intermediate; (7) impregnating the catalyst intermediate obtained in step (6) with the impregnation solution C, and then adding a polyether nonionic surfactant, and then performing ultrasonic treatment, and then drying and calcining to obtain a hydrogenation catalyst. In step (5), the oil phase is maintained in a liquid state at a temperature of 45-85℃.

2. The method of claim 1, wherein, In step (1), the surfactant is selected from one or more of glycerol monostearate, glycerol distearate, glycerol monolaurate, and polyoxyethylene ether fatty alcohol; the oil is at least one of a silicone oil and a vegetable oil, the silicone oil is 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 one or more of peanut oil, coconut oil, and tea seed oil.

3. The method of claim 1, wherein, In step (1), the heating is to a temperature of 40-80℃, and / or, in step (1), the mass ratio of the surfactant to the oil is 1.0:0.1-10.

4. The method of claim 3, wherein, In step (1), the mass ratio of the surfactant to the oil is 1.0:2-10.

5. The method of claim 1, wherein, In step (2), the emulsifying assistant is selected from one or more of polyethylene glycol-8000, polyethylene glycol-400, cetyl alcohol, stearyl alcohol, propylene glycol, n-butanol, polyvinyl alcohol, and glycerol; and / or, in step (2), the amount of the emulsifying assistant is 0.5%-5.0% of the mass of the aqueous phase obtained in step (4).

6. The method of claim 1, wherein, In step (2), 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; and the phosphorus source is one or more of phosphoric acid, monobasic ammonium phosphate, and dibasic ammonium phosphate.

7. The method of claim 6, wherein, In the active metal impregnation solution in step (3), the mass concentration of phosphorus as an oxide is 1.0%-8.0%.

8. The method of claim 1, wherein, In step (2), the heating is to a temperature of 90-120℃.

9. The method of claim 1, wherein, In step (3), the Group VIII metal is Ni and / or Co.

10. The method of claim 9, wherein, In the active metal impregnation solution in step (3), the concentration of the Group VIB metal as an oxide is 8-80 g / 100 mL, and the concentration of the Group VIII metal as an oxide is 2-50 g / 100 mL.

11. The method of claim 10, wherein, In step (3), the concentration of the Group ⅥB metal in the active metal impregnation solution is 10-60 g / 100 mL as oxide, and the concentration of the Group Ⅷ metal is 5-30 g / 100 mL as oxide.

12. The method of claim 1, wherein, In step (3), the volume ratio of the impregnation solution A to the impregnation solution B is 0.1-6.

0.

13. The method of claim 12, wherein, In step (3), the volume ratio of the impregnation solution A to the impregnation solution B is 0.25-5.

0.

14. The method of claim 1, wherein, In step (4), the water-soluble high polymer is one or more of polyvinyl alcohol, carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate.

15. The method of claim 14, wherein, In step (4), the mass concentration of the water-soluble high polymer in the aqueous phase is 4.0-14.0%.

16. The method of claim 1, wherein, In step (5), the stirring speed for keeping the oil phase in a liquid state is 400-800 r / min.

17. The method of claim 1, wherein, In step (5), the mass ratio of the aqueous phase to the oil phase is 0.4-8.0:1.0; and / or, in step (5), the stirring speed for shearing and homogenizing is 10,000-18,000 rpm, the shearing and homogenizing time is 3-8 min, and the temperature during the shearing and homogenizing is 50-85℃.

18. The method of claim 17, wherein, In step (5), the mass ratio of the aqueous phase to the oil phase is 0.5-5.0:1.

0.

19. The method of claim 1, wherein, In step (5), the particle size of the water-in-oil small droplets in the impregnation solution C is 5-20 nm.

20. The method of claim 1, wherein, In step (6), the carrier dry gel powder is a carrier dry gel powder for a residual oil hydrodemetallization catalyst, and the hydrogenation catalyst is a residual oil hydrodemetallization catalyst.

21. The method of claim 20, wherein, In step (6), the dried carrier gel powder after high-temperature calcination has the following properties: specific surface area of 150-350 m 2 / g, pore volume of 0.3-1.0 cm 3 / g, and the pore volume of pores of 10-30 nm in the pore distribution is more than 30% of the total pore volume.

22. The method of claim 21, wherein, In step (6), after high-temperature calcination, the carrier dry gel powder has the following properties: the pore volume of pores with a size of 10-30 nm accounts for 40%-80% of the total pore volume.

23. The method of claim 1, wherein, In step (7), the polyether non-ionic surfactant is one or more of a fatty alcohol polyvinyl chloride ether, an ester polyvinyl chloride ether, a phenolic polyvinyl chloride ether, and a fatty amine polyvinyl chloride ether.

24. The method of claim 23, wherein, In step (7), the amount of the polyether non-ionic surfactant is 2.5%-7.5% of the mass of the impregnation solution C.

25. The method of claim 1, wherein, In step (7), the impregnation method is an excess impregnation method, in which the liquid-to-solid volume ratio of the impregnation solution C to the catalyst intermediate is 2.0-8.0; and / or, in step (7), the ultrasonic treatment conditions are as follows: the ultrasonic frequency is 15-35 kHz, the material temperature during the treatment is 35-75℃, and the time is 15-60 min; and / or, in step (7), the drying temperature is 80℃-180℃, the drying time is 2-8 h, the calcination temperature is 450℃-700℃, and the calcination time is 2-8 h.

26. A hydrogenation catalyst prepared by the method of any one of claims 1-25.

27. The hydrogenation catalyst of claim 26, wherein, The hydrogenation catalyst is a residual oil hydrodemetallization catalyst.

28. The hydrogenation catalyst of claim 26, wherein, In the hydrogenation catalyst, the content of the Group VIB metal as oxide is 6.0%-26.0% based on the mass of the hydrogenation catalyst, and the content of the Group VIII metal as oxide is 2.0%-14.0%.

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