A hydrogenation catalyst impregnation solution and a method for preparing the hydrogenation catalyst.

Abstract

This invention discloses a hydrogenation catalyst impregnation solution and a method for preparing the hydrogenation catalyst. The hydrogenation catalyst impregnation solution comprises an aqueous phase and an oil phase coating the aqueous phase. The aqueous phase includes an active metal source, a co-emulsifier, a water-soluble polymer, water, and optionally a phosphorus source. The active metal includes Group VIB metals and / or Group VIII metals. The oil phase includes a surfactant and oil, with a surfactant-to-oil mass ratio of 1.0:0.1-10. The residue oil hydrogenation metal catalyst prepared using the impregnation solution of this invention can improve the hydrogenation activity and stability of the catalyst.

Description

Technical Field

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

[0002] Currently, the degree of heavy and inferior crude oil quality is increasing worldwide, while the market demand for light oil products is also growing daily. Heavy oil hydrotreating technology is gradually becoming a focus of attention in the petrochemical industry. Fixed-bed residue hydrotreating technology is mature and widely used, serving as 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 hydrodemetallization catalyst occupies a relatively prominent position in the fixed-bed residue hydrotreating catalyst gradation system and bears a significant reaction load, developing a hydrotreating catalyst with a longer lifespan and better hydrotreating performance, especially a hydrodemetallization catalyst, is particularly important.

[0003] Currently, research on hydrogenation catalysts mainly focuses on two aspects: supports and active metal loading. Conventional impregnation methods are usually used for active metal loading, which results in limited dispersion of active metals on the catalyst, poor hydrogenation performance, and poor resistance to metal deposition and carbon buildup.

[0004] CN102600913A discloses a method for preparing an aqueous solution for impregnation with molybdenum, nickel, and phosphorus. The method involves first preparing an aqueous solution containing soluble molybdenum, nickel, and phosphorus, 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 method offers advantages such as adjustable molybdenum-nickel ratio, simple preparation process, large dissolution capacity, and long stability time, and can be used to prepare impregnation solutions for hydrogenation catalysts.

[0005] CN104646007A discloses a residue oil hydrodemetallization catalyst, its preparation method, and its application. The method includes: firstly, pretreating an activated carbon support with hydrochloric acid washing and nitric acid oxidation; then, mixing and extruding a composite additive, activated carbon, and alumina to prepare an activated carbon / alumina composite; finally, loading metal onto the support using a hydrotalcite method, i.e., impregnating 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), crystallizing, washing several times, and drying 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 dried and calcined to obtain the residue oil hydrodemetallization catalyst.

[0006] CN20110317245.3 discloses an impregnation solution for a hydrogenation catalyst and a method for preparing the same. The method includes: preparing an aqueous solution A from a Group VIII metal compound and a first organic complexing agent; preparing an aqueous solution B from a Group VIB metal compound; and then mixing the aqueous solutions A and B; wherein the ligand of the first organic complexing agent contains at least a coordinating atom N.

[0007] 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.

[0008] 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.

[0009] 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

[0010] To address the shortcomings of existing technologies, this invention provides a hydrogenation catalyst impregnation solution and a method for preparing the hydrogenation catalyst. The residue oil hydrogenation metal catalyst prepared using the impregnation solution of this invention can improve the hydrogenation activity and stability of the catalyst.

[0011] The first aspect of the present invention provides a hydrogenation catalyst impregnation solution, comprising an aqueous phase and an oil phase coating the aqueous phase. The aqueous phase comprises an active metal source, a co-emulsifier, a water-soluble polymer, and water, and optionally a phosphorus source. The active metal comprises a Group VIB metal and / or a Group VIII metal. The oil phase comprises a surfactant and oil, wherein the mass ratio of surfactant to oil is 1.0:0.1 to 10, preferably 1.0:2 to 10, and more preferably 1.0:4 to 10.

[0012] In the impregnation solution of the hydrogenation catalyst of the present invention, the mass ratio of the aqueous phase to the oil phase is 0.4 to 12.0:1.0, preferably 0.5 to 9.0:1.0, for example 0.5:1.0, 0.7:1, 0.9:1.0, 1.0:1.0, 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 any range formed by any two of these values.

[0013] In the impregnation solution of the hydrogenation catalyst of the present 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).

[0014] In the hydrogenation catalyst impregnation solution of the present invention, the mass concentration of the water-soluble polymer in the aqueous phase is 4.0% to 14.0%.

[0015] In the impregnation solution of the hydrogenation catalyst of the present invention, the aqueous phase contains a concentration of Group VIB metals (based on oxides) of 8-80 g / 100 ml, preferably 10-60 g / 100 ml, and a concentration of Group VIII metals (based on oxides) of 2-50 g / 100 ml, preferably 5-30 g / 100 ml.

[0016] In the impregnation solution of the hydrogenation catalyst of this invention, the Group VIB metal is Mo and / or W, and the Group VIII metal is Ni and / or Co. The Group VIB metal source is one or more of ammonium molybdate, ammonium metatungstate, and molybdenum oxide. The Group VIII metal source is one or more of basic nickel nitrate, cobalt nitrate, etc.

[0017] In the impregnation solution of the hydrogenation catalyst of the present invention, the aqueous phase further includes phosphorus, and the phosphorus source is one or more of phosphoric acid, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate. The mass concentration of phosphorus in the aqueous phase, calculated as oxides, is 1.0% to 8.0%.

[0018] In the impregnation solution of the hydrogenation catalyst of this invention, the co-emulsifier is selected from one or more of polyethylene glycol-8000, polyethylene glycol-400, cetyl alcohol, octadecyl alcohol, propylene glycol, n-butanol, and glycerol. In the aqueous phase, the mass concentration of the co-emulsifier is 0.5% to 5.0%.

[0019] In the impregnation solution of the hydrogenation catalyst of this invention, the surfactant is selected from glyceryl monostearate, glyceryl distearate, glyceryl monolaurate, and polyoxyethylene ether fatty alcohol (structure R-(OCC)). x -OH, where R is a straight-chain alkyl group with 12 to 15 carbon atoms, and x is 2 to 11, etc.

[0020] In the hydrogenation catalyst impregnation solution of this invention, the oil is selected from at least one of silicone oil and vegetable oil. The silicone oil may be at least one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen silicone oil, and methylphenyl silicone oil. The vegetable oil is selected from one or more of peanut oil, coconut oil, and tea seed oil.

[0021] In the impregnation solution of the hydrogenation catalyst of this invention, the particle size of the water-in-oil droplets is 5-20 nm.

[0022] A second aspect of the present invention provides a method for preparing the above-mentioned impregnation solution, comprising:

[0023] (1) Add the surfactant to the oil and heat it to obtain the oil phase;

[0024] (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;

[0025] (3) Add the Group VIII metal source to the clear solution obtained in step (2);

[0026] (4) Add a water-soluble polymer to the mixture obtained in step (3) to obtain an aqueous phase;

[0027] (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, the mixture is stirred, sheared, and homogenized to obtain the impregnation solution.

[0028] 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.

[0029] In step (1), the temperature is heated to 40-80°C to make the oil phase appear as a uniform liquid.

[0030] 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.

[0031] 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.

[0032] 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).

[0033] In step (2), the Group VIB metal source can be one or more of molybdenum oxide, ammonium tetramolybdate, ammonium metatungstate, and ammonium heptamolybdate. The phosphorus source can be one or more of phosphoric acid, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate.

[0034] In step (2), the water is distilled water or deionized water, and the conductivity of the water should be less than 10.0 mS.

[0035] 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.

[0036] 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.

[0037] In step (4), the concentration of Group VIB metals as oxides in the aqueous phase 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.

[0038] In step (4), the water-soluble polymer is one or more of polyvinyl alcohol, carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate.

[0039] In step (4), the mass concentration of the water-soluble polymer in the aqueous phase is 4.0 to 14.0%.

[0040] 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.

[0041] In step (5), the mass ratio of the aqueous phase to the oil phase is 0.4 to 12.0:1.0, preferably 0.5 to 9.0:1.0.

[0042] 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.

[0043] The third aspect of the present invention provides a method for preparing a hydrogenation catalyst, comprising: impregnating a support with the above-mentioned impregnation solution, allowing it to stand, then adding a polyether-type nonionic surfactant, followed by ultrasonic treatment, drying, and calcination to obtain a hydrogenation catalyst.

[0044] In the preparation method of the hydrogenation catalyst of the present invention, 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.

[0045] In the preparation method of the hydrogenation catalyst of the present invention, the amount of the polyether-type nonionic surfactant is 2.5% to 7.5% of the mass of the impregnation solution.

[0046] In the preparation method of the hydrogenation catalyst of this invention, the support can be any of the commonly used supports in the art, such as alumina, silicon dioxide, titanium dioxide, magnesium oxide, zirconium oxide, or a composite support, or one or more of these. Support materials with different average pore sizes can be selected as needed, and the shape of the support particles is not further limited; they can be clover-shaped, trefoil-shaped, cylindrical, etc. Preferably, the support is a catalyst support for the hydrodemetallization of residue oil, and the hydrogenation catalyst is a hydrodemetallization catalyst for residue oil. The support is preferably an alumina-based support with a 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%-70%.

[0047] In the preparation method of the hydrogenation catalyst of the present invention, the impregnation method is an excess impregnation method. The liquid-to-solid volume ratio of the hydrogenation impregnation solution to the support is 2.0–8.0. The impregnated sample is left to stand at room temperature for 1–12 hours.

[0048] In the preparation method of the hydrogenation catalyst of the present invention, the ultrasonic treatment conditions are as follows: the ultrasonic frequency is 15-35 kHz, the material temperature is 35-75 °C, and the time is 15-60 min.

[0049] In the preparation method of the hydrogenation catalyst of the present invention, 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 an oxygen-containing atmosphere, preferably air.

[0050] In the preparation method of the hydrogenation catalyst of the present invention, the hydrogenation catalyst contains, based on the mass of the hydrogenation catalyst, 6.0% to 26.0% of Group VIB metals as oxides and 2.0% to 14.0% of Group VIII metals as oxides.

[0051] Compared with the prior art, the present invention has the following beneficial effects:

[0052] 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.

[0053] The hydrogenation catalyst impregnation solution of this invention utilizes 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 surface and within the pores of the support. In this invention, the "water-in-oil" droplets can penetrate deep into the pores and surface of the support. Furthermore, by introducing a polyether-type nonionic surfactant, the "surface layer" on the particle surface can be removed. Combined with ultrasonic treatment, the aqueous phase can detach from the oil-based dispersion matrix and uniformly adsorb into the internal pores and surface of the support. Finally, after drying and calcination, the resulting impregnated support yields a hydrogenation catalyst with a more uniform dispersion of the active metal.

[0054] 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

[0055] 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.

[0056] Example 1

[0057] 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 20:265:58.5:64.8:70.3:400. The mass ratio of oil phase to water phase is 900:880.

[0058] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0059] (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;

[0060] (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.

[0061] (3) Add basic nickel carbonate to the clear solution obtained in step (2);

[0062] (4) Add water-soluble polymer polyvinyl alcohol to the mixture obtained in step (3) to obtain an aqueous phase;

[0063] (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 the mixture is stirred. 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 is obtained.

[0064] (6) Apply the impregnation solution obtained in step (5) to the catalyst support (alumina support, with a specific surface area of ​​203 m²). 2 / g, pore volume is 0.81cm 3 / g, with pores of 10-30nm accounting for 58.2% of the total pore volume) were impregnated at a volume ratio of 5.0, and allowed to stand for 18 hours. Then, fatty alcohol polyvinyl chloride ether (R = 12, x = 5) was added at a volume of 3.5% of the impregnation solution mass. The mixture was then ultrasonically treated for 30 minutes at a frequency of 25kHz, with the material temperature maintained at 70℃ during the treatment. This allowed the aqueous phase to separate from the oil phase, while the oil phase gradually accumulated. After phase separation, the mixture was first dried at 120℃ for 6 hours and then calcined at 550℃ 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.

[0065] Example 2

[0066] 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), and water-soluble polymer to water is 24:265:58.5:64.8:90.3:400. The mass ratio of oil phase to water phase is 920:903.

[0067] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0068] (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;

[0069] (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.

[0070] (3) Add basic nickel carbonate to the clear solution obtained in step (2);

[0071] (4) Add water-soluble polymer carboxymethyl cellulose to the mixture obtained in step (3) to obtain an aqueous phase;

[0072] (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 is obtained.

[0073] (6) Apply the impregnation solution obtained in step (5) to the catalyst support (alumina support, with a specific surface area of ​​203 m²). 2 / g, pore volume is 0.81cm 3 / g, with pores of 10-30nm accounting for 58.2% of the total pore volume) were impregnated at a volume ratio of 5.0, and allowed to stand for 18h. Then, fatty alcohol polyvinyl chloride ether (R = 12, x = 5) was added at a volume of 4.5% of the impregnation solution mass. The mixture was then ultrasonically treated for 40min at a frequency of 30kHz, with the material temperature at 60℃ during the treatment. This allowed the aqueous phase to separate from the oil phase, while the oil phase gradually accumulated. After phase separation, the mixture was first dried at 120℃ for 6h and then calcined at 550℃ for 4h 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.

[0074] Example 3

[0075] 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 28:265:58.5:64.8:111.3:400. The mass ratio of oil phase to water phase is 940:928.

[0076] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0077] (1) Add the surfactant glyceryl monolaurate to the silicone oil, heat to 70°C, and wait for the silicone oil to melt to obtain the oil phase;

[0078] (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.

[0079] (3) Add basic nickel carbonate to the clear solution obtained in step (2);

[0080] (4) Add water-soluble polymer sodium polyacrylate to the mixture obtained in step (3) to obtain an aqueous phase;

[0081] (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 the mixture is stirred. 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 is obtained.

[0082] (6) Apply the impregnation solution obtained in step (5) to the catalyst support (alumina support, with a specific surface area of ​​203 m²). 2 / g, pore volume is 0.81cm 3 / g, with pores of 10-30nm accounting for 58.2% of the total pore volume) were impregnated at a volume ratio of 5.0, and allowed to stand for 18 hours. Then, fatty alcohol polyvinyl chloride ether (R = 12, x = 5) was added at a volume of 5.5% of the impregnation solution mass. The mixture was then ultrasonically treated for 50 minutes at a frequency of 20kHz, with the material temperature maintained at 50℃ during the treatment. This allowed the aqueous phase to separate from the oil phase, while the oil phase gradually accumulated. After phase separation, the mixture was first dried at 120℃ for 6 hours and then calcined at 550℃ 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.

[0083] Example 4

[0084] 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 28:265:58.5:64.8:51.3:400. The mass ratio of oil phase to water phase is 880:856.

[0085] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0086] (1) Add the surfactant polyoxyethylene ether fatty alcohol to the silicone oil, heat to 65°C, and wait for the silicone oil to melt to obtain the oil phase;

[0087] (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.

[0088] (3) Add basic nickel carbonate to the clear solution obtained in step (2);

[0089] (4) Add water-soluble polymer gelatin to the mixture obtained in step (3) to obtain an aqueous phase;

[0090] (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 is obtained.

[0091] (6) Apply the impregnation solution obtained in step (5) to the catalyst support (alumina support, with a specific surface area of ​​203 m²). 2 / g, pore volume is 0.81cm 3 / g, with pores of 10-30nm accounting for 58.2% of the total pore volume) were impregnated at a volume ratio of 5.0, and allowed to stand for 18 hours. Then, fatty alcohol polyvinyl chloride ether (R = 12, x = 5) was added at a volume of 6.5% of the impregnation solution mass. The mixture was then ultrasonically treated for 20 minutes at a frequency of 15kHz, with the material temperature maintained at 40℃ during the treatment. This allowed the aqueous phase to separate from the oil phase, while the oil phase gradually accumulated. After phase separation, the mixture was first dried at 120℃ for 6 hours and then calcined at 550℃ 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 experimental results of the catalyst are shown in Table 4.

[0092] Comparative Example 1

[0093] 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.

[0094] Comparative Example 2

[0095] 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.

[0096] Comparative Example 3

[0097] 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.

[0098] Comparative Example 4

[0099] 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.

[0100] Comparative Example 5

[0101] The difference from Example 1 is that no water-soluble polymer was added to the mixture in step (4) (derived from step (3)). The final catalyst obtained was dCAT-5. The properties of the resulting impregnation solution and catalyst are shown in Table 2, and the test results of the catalyst are shown in Table 5.

[0102] Comparative Example 6

[0103] 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), and water is 20:265:58.5:64.8:400. The mass ratio of oil phase to water phase is 900:880.

[0104] The method for preparing the hydrogenation demetallization catalyst in this example is as follows:

[0105] (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.

[0106] (2) Add basic nickel carbonate to the clear solution obtained in step (1) to obtain an aqueous phase;

[0107] (3) Add the surfactant glyceryl monostearate, silicone oil, and co-emulsifier polyethylene glycol-8000 to the aqueous phase 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 impregnation solution is obtained.

[0108] (4) The catalyst support (same as in Example 1) was impregnated with the impregnation solution obtained in step (3) at a volume ratio of 5.0, 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 obtained impregnation solution and catalyst are shown in Table 2, and the test results of the catalyst are shown in Table 5.

[0109] Comparative Example 7

[0110] 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.

[0111] Table 1. Physicochemical properties of the impregnation solutions and catalysts obtained in each embodiment.

[0112]

[0113]

[0114] Table 2. Physicochemical properties of the impregnation solutions and catalysts obtained in each comparative example.

[0115]

[0116] Application examples

[0117] 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 370 °C, reaction pressure 15.0 MPa, and liquid hourly space velocity 1.0 h⁻¹. -1 With a hydrogen-to-oil volume ratio of 750, 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.

[0118] Table 3 Properties of Feed Oil

[0119] Item <![CDATA[Density at 20°C, kg / m 3 > 970.0 S, wt% 2.34 N, wt% 0.45 Ni, μg / g 31.1 V, μg / g 68.5 CCR, wt% 12.5

[0120] Table 4 shows the test results of the catalysts obtained in each example.

[0121]

[0122] Table 5 shows the experimental results of the catalysts obtained in each comparative example.

[0123]

[0124] 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 hydrogenation catalyst impregnation solution comprising an aqueous phase and an oil phase coating the aqueous phase, wherein the aqueous phase comprises an active metal source, a co-emulsifier, a water-soluble polymer, and water, and optionally a phosphorus source, wherein the active metal comprises a Group VIB metal and / or a Group VIII metal; the oil phase comprises a surfactant and oil, wherein the mass ratio of surfactant to oil is 1.0:0.1~10; and the mass ratio of aqueous phase to oil phase is 0.4~12.0:1.

0.

2. The impregnation solution according to claim 1, characterized in that, In the oil phase, the mass ratio of surfactant to oil is 1.0:2~10.

3. The impregnation solution according to claim 1, characterized in that, The mass ratio of the aqueous phase to the oil phase is 0.5~9.0:1.

0.

4. The impregnation solution according to claim 1, characterized in that, The water-soluble polymer is one or more of polyvinyl alcohol, carboxymethyl cellulose, gelatin, gum arabic, and sodium polyacrylate; and / or, the mass concentration of the water-soluble polymer in the aqueous phase is 4.0% to 14.0%.

5. The impregnation solution according to claim 1, characterized in that, In the aqueous phase, the concentration of Group VIB metals as oxides is 8~80 g / 100 mL, and the concentration of Group VIII metals as oxides is 2~50 g / 100 mL.

6. The impregnation solution according to claim 5, characterized in that, In the aqueous phase, the concentration of Group VIB metals as oxides is 10~70 g / 100 mL, and the concentration of Group VIII metals as oxides is 5~30 g / 100 mL.

7. The impregnation solution according to claim 1, characterized in that, Group VIB metals are Mo and / or W, and Group VIII metals are Ni and / or Co.

8. The impregnation solution according to claim 7, characterized in that, Group VIB metal sources are one or more of ammonium molybdate, ammonium metatungstate, and molybdenum oxide, while Group VIII metal sources are one or more of basic nickel nitrate and cobalt nitrate.

9. The impregnation solution according to claim 1, characterized in that, In the aqueous phase, the phosphorus source is one or more of phosphoric acid, ammonium monohydrogen phosphate, and ammonium dihydrogen phosphate; and / or, the co-emulsifier is selected from one or more of polyethylene glycol-8000, polyethylene glycol-400, cetyl alcohol, octadecanol, propylene glycol, n-butanol, and glycerol.

10. The impregnation solution according to claim 9, characterized in that, In the aqueous phase, the mass concentration of phosphorus as oxide is 1.0% to 8.0%; in the aqueous phase, the mass concentration of co-emulsifier is 0.5% to 5.0%.

11. The impregnation solution according to claim 1, characterized in that, The surfactant is selected from one or more of glyceryl monostearate, glyceryl distearate, glyceryl monolaurate, and polyoxyethylene ether fatty alcohol; and / or, the oil is selected from at least one of silicone oil and vegetable oil, wherein 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 selected from one or more of peanut oil, coconut oil, and tea seed oil.

12. The impregnation solution according to claim 1, characterized in that, The particle size of the water-in-oil droplets is 5~20nm.

13. A method for preparing the impregnation solution according to any one of claims 1-12, comprising: (1) Add the surfactant to the oil and heat it to obtain the oil phase; (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; (3) Add the Group VIII metal source to the clear solution obtained in step (2); (4) Add a water-soluble polymer to the mixture obtained in step (3) to obtain an aqueous phase; (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.

14. The preparation method according to claim 13, characterized in that, In step (1), the heating temperature is 40~80℃; and / or, in step (2), the heating temperature is 90~120℃; and / or, in step (5), the oil phase is kept in a liquid state at a temperature of 45~85℃ and the stirring rate is 400~800r / min.

15. The preparation method according to claim 13, characterized in that, 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.

16. A method for preparing a hydrogenation catalyst, comprising: The carrier is impregnated with the impregnation solution according to any one of claims 1-12, allowed to stand, then a polyether-type nonionic surfactant is added, followed by ultrasonic treatment, drying, and calcination to obtain a hydrogenation catalyst.

17. The preparation method according to claim 16, characterized in that, 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.

18. The preparation method according to claim 17, characterized in that, The amount of the polyether-type nonionic surfactant used is 2.5% to 7.5% of the mass of the impregnation solution.

19. The preparation method according to claim 16, characterized in that, The support is a residue oil hydrodemetallization catalyst support, and the hydrodemetallization catalyst is a residue oil hydrodemetallization catalyst.

20. The preparation method according to claim 16, characterized in that, The impregnation method is an over-impregnation method; and / or, the drying temperature is 80℃~180℃, the drying time is 2~8h, and the calcination temperature is 450℃~700℃, the calcination time is 2~8h.

21. The preparation method according to claim 16, characterized in that, The ultrasonic treatment conditions are as follows: ultrasonic frequency is 15~35kHz, material temperature is 35~75℃, and treatment time is 15~60min.

22. The preparation method according to claim 16, characterized in that, 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%.

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